Stable emulsion formulations of encapsulated volatile compounds

ABSTRACT

The present invention is based on the discovery of a stable water-in-oil-in-water double emulsion. The double emulsion composition disclosed may contain molecular complex of volatile compounds for example 1-methylcyclopropene (1-MCP). In addition, the double emulsion composition disclosed can provide prolong or controlled release of the volatile compounds.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit under 35 USC § 119(e) of U.S.Provisional Application Ser. No. 62/157,588, filed on May 6, 2015, theentire disclosure of which is incorporated herein by reference.

BACKGROUND OF THE INVENTION

Various compounds can be encapsulated using certain molecularencapsulating agents. Encapsulation provides a means to control thedelivery of these compounds into the matrix of use. For example,volatile cyclopropene compounds are known to be encapsulated usingcyclodextrins. Cyclopropene compounds are useful for treating plants orplant parts. As a way of storing cyclopropenes or of delivering them toplant parts, or both, it is sometimes useful to form complexes ofcyclopropene molecules with molecular encapsulating/complexing agents.It is also known that contacting encapsulated cyclopropene with asolvent (for example tap water) can quickly release cyclopropenemolecules from the complex into air space. Thus, liquid (especiallyaqueous) formulations of encapsulated cyclopropene compounds aretypically unstable for storage purpose.

1-Methylcyclopropene (1-MCP) is a gas difficult to handle and store; itis also flammable above a concentration of 13,300 parts per million(ppm). As a result, in current agriculture applications, 1-MCP isusually stabilized into a clathrate such as α-cyclodextrin(alpha-cyclodextrin or α-CD) to ease handling during storage andtransportation. The active ingredient 1-MCP is caged in α-CD, and theresulting crystalline complex is called a High Active Ingredient Product(HAIP). HAIP is typically composed of 100-150 micron (μm) needle-likecrystals but can be air-milled to a 3-5 μm fine powder if needed. HAIPproduct can be stored for up to two years at ambient temperature insidea sealed container lined with a moisture barrier without loss of 1-MCP.Although the product is more convenient for the application than the1-MCP gas itself, it still has some disadvantages: (1) it is in a powderform and thus is difficult to handle in the field or in an enclosedspace; and (2) it is water-sensitive, and releases 1-MCP gas completelywithin a short period of time when in contact with water. Upon contactwith water or even moisture, 1-MCP gas will be quickly released at arate which is not compatible with tank use as most of the gas will belost in the tank headspace before the product has a chance to be sprayedin the field.

As provided herein, a stable water-in-oil (W/O) emulsion can be madewith water based dispersion of HAIP (containing magnesium sulfate,polyvinyl alcohol, and other ingredients) in various oils (for examplesoybean oil) containing emulsifiers. An aqueous dispersion of HAIP(containing >7 grams (g) of 1-MCP per liter (/L)) can be used to makestable water-in-oil dispersions where the 1-MCP concentration is <4 g/Lor <10 g/L. Their formulations may have <5,000 ppm of 1-MCP in theheadspace.

It is well known that adding water to HAIP (nominally 4.5% 1-MCP)rapidly releases 1-MCP. Hence to design a stable product concentratewith HAIP that can be diluted with water in the field or a ready-to-useproduct with low active ingredient (AI), it will be important to isolatethe HAIP from the continuous water phase. One way of achieving this isvia emulsion technology, specifically utilizing a water-in-oil-in-wateremulsification approach.

Accordingly, there remains a need to develop stable liquid formulationsfor encapsulated volatile compounds, especially for long term storage ofconcentrated formulations which can be diluted with water before fieldapplications.

SUMMARY OF THE INVENTION

The present invention is based on the discovery of a stablewater-in-oil-in-water double emulsion in addition to a stableaqueous-in-oil emulsion. The double emulsion composition provided and/orthe stable aqueous-in-oil emulsion disclosed may contain molecularcomplexes of volatile compounds for example 1-methylcyclopropene(1-MCP). In addition, the double emulsion composition provided and/orthe stable aqueous-in-oil emulsion disclosed can provide prolonged orcontrolled release of the volatile compounds. Due to its unexpectedstability, the double emulsion composition disclosed can also be used asa stock solution or concentrated solution to be further diluted withwater as sprayable or oral formulations.

Other objects, features and advantages of the present invention willbecome apparent from the following detailed description. It should beunderstood, however, that the detailed description and the specificexamples, while indicating specific embodiments of the invention, aregiven by way of illustration only, since various changes andmodifications within the spirit and scope of the invention will becomeapparent to those skilled in the art from this detailed description.

The following numbered embodiments are contemplated and arenon-limiting:

-   -   1. An aqueous-in-oil-in-aqueous double emulsion composition        comprising:        -   (a) an aqueous-in-oil emulsion composition;        -   (b) a hydrophilic emulsifier;        -   (c) a surfactant; and        -   (d) a second aqueous phase.    -   2. The aqueous-in-oil-in-aqueous double emulsion composition of        clause 1, wherein the aqueous-in-oil emulsion composition        comprises an aqueous phase containing salt (APCS).    -   3. The aqueous-in-oil-in-aqueous double emulsion composition of        clause 2, wherein the APCS comprises water.    -   4. The aqueous-in-oil-in-aqueous double emulsion composition of        clause 2 or clause 3, wherein the APCS comprises water at an        amount selected from the group consisting of more than 20% water        by weight, more than 30% water by weight, more than 50% water by        weight, and more than 60% water by weight (based on the weight        of the composition).    -   5. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 2 to 4, wherein the APCS comprises one or        more salts.    -   6. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 2 to 5, wherein no chloride salt is used.    -   7. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 2 to 6, wherein the salt is a        non-deliquescent salt.    -   8. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 2 to 7, wherein the salt is dissolved in the        aqueous phase.    -   9. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 2 to 8, wherein the salt comprises magnesium        sulfate or ammonium sulfate.    -   10. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 2 to 8, wherein the salt comprises magnesium        sulfate.    -   11. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 2 to 8, wherein the salt comprises ammonium        sulfate.    -   12. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 2 to 11, wherein the salt comprises magnesium        sulfate or ammonium sulfate the ratio of dry weight of the salt        to weight of the aqueous phase of the aqueous-in-oil emulsion        composition is at least 0.25.    -   13. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 2 to 11, wherein the salt comprises magnesium        sulfate or ammonium sulfate the ratio of dry weight of the salt        to weight of the aqueous phase of the aqueous-in-oil emulsion        composition is at least 0.3.    -   14. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 2 to 11, wherein the salt comprises magnesium        sulfate or ammonium sulfate the ratio of dry weight of the salt        to weight of the aqueous phase of the aqueous-in-oil emulsion        composition is at least 0.35.    -   15. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 2 to 11, wherein the ratio of the dry weight        of salt to the weight of water is selected from the group        consisting of 0.05 or higher; or 0.1 or higher; or 0.2 or        higher; or 0.3 or higher; or 0.35 or higher.    -   16. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 2 to 15, wherein the APCS comprises an active        ingredient.    -   17. The aqueous-in-oil-in-aqueous double emulsion composition of        clause 16, wherein the active ingredient comprises a molecular        complex of an encapsulated volatile compound.    -   18. The aqueous-in-oil-in-aqueous double emulsion composition of        clause 17, wherein the composition has the molecular complex of        the encapsulated volatile compound distributed throughout the        aqueous-in-oil emulsion composition.    -   19. The aqueous-in-oil-in-aqueous double emulsion composition of        clause 17 or clause 18, wherein the ratio of dry weight of the        salt to dry weight of the molecular complex of the encapsulated        volatile compound is from 0.03 to 500.    -   20. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 17 to 19, wherein the molecular complex of an        encapsulated volatile compound comprises a cyclopropene        molecular encapsulating agent complex.    -   21. The aqueous-in-oil-in-aqueous double emulsion composition of        clause 20, wherein the cyclopropene is of the formula:

wherein R is a substituted or unsubstituted alkyl, alkenyl, alkynyl,cycloalkyl, cycloalkylalkyl, phenyl, or naphthyl group; wherein thesubstituents are independently halogen, alkoxy, or substituted orunsubstituted phenoxy.

-   -   22. The aqueous-in-oil-in-aqueous double emulsion composition of        clause 20, wherein the cyclopropene is of the formula

-   -   wherein R¹ is a substituted or unsubstituted C₁-C₄ alkyl, C₂-C₄        alkenyl, C₂-C₄ alkynyl, C₃-C₆ cycloalkyl, cycloalkylalkyl,        phenyl, or napthyl group; and R², R³, and R⁴ are hydrogen.    -   23. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 20 to 22, wherein the cyclopropene is        1-methylcyclopropene (1-MCP).    -   24. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 20 to 23, wherein the molecular encapsulating        agent is alpha-cyclodextrin.    -   25. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 20 to 24, wherein the double emulsion        composition comprises at least 5%, at least 10%, at least 20%,        at least 30%, at least 40%, at least 50%, or at least 60% by        weight of a complex of 1-methylcyclopropene (1-MCP) and        alpha-cyclodextrin.    -   26. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 1 to 25, wherein the aqueous-in-oil emulsion        composition comprises an oil phase comprising an oil medium.    -   27. The aqueous-in-oil-in-aqueous double emulsion composition of        clause 26, wherein the oil medium is selected from the group        consisting of soybean oil, hydrogenated soybean oil, cotton seed        oil, hydrogenated cotton seed oil, white mineral oil,        hydrotreated middle petroleum distillate, hydrotreated light        petroleum distillate, and combinations thereof.    -   28. The aqueous-in-oil-in-aqueous double emulsion composition of        clause 26 or clause 27, wherein the aqueous-in-oil emulsion        composition comprises 10-20%; 20-40%; 40-60%; 15-30%; or 30-55%        by weight of the oil phase.    -   29. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 2 to 28, wherein the aqueous-in-oil emulsion        composition comprises a lipophilic emulsifier.    -   30. The aqueous-in-oil-in-aqueous double emulsion composition of        clause 29, wherein the lipophilic emulsifier is selected from        the group consisting of polyglycerol polyricinoleate, lecithin,        sorbitan fatty esters, and combinations thereof.    -   31. The aqueous-in-oil-in-aqueous double emulsion composition of        clause 29 or clause 30, wherein the lipophilic emulsifier is        polyglycerol polyricinoleate (PGPR).    -   32. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 2 to 28, wherein the aqueous-in-oil emulsion        composition comprises an oil soluble thickener.    -   33. The aqueous-in-oil-in-aqueous double emulsion composition of        clause 32, wherein the oil soluble thickener is selected from        the group consisting of natural rubber, polypropylene,        polyisoprene, polybutadiene, poly(styrene-butadiene),        poly(ethylene-propylene-diene), polyurethane, polymethacrylate,        polyisobutylene, poly(isobutylene-succinic acid),        poly(isobutylene-succinic acid-polyacrylamide), polyurea,        polyethylene, and combinations thereof.    -   34. The aqueous-in-oil-in-aqueous double emulsion composition of        clause 32 or clause 33, wherein the oil soluble thickener is a        (co- or homo)polymer of propylene.    -   35. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 1 to 34, wherein the second aqueous phase        comprises water.    -   36. The aqueous-in-oil-in-aqueous double emulsion composition of        clause 35, wherein water is present at a ratio of aqueous-in-oil        emulsion composition:water from 1:1 to 1:100.    -   37. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 1 to 36, wherein the hydrophilic emulsifier        is present in the second aqueous phase.    -   38. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 1 to 37, wherein the hydrophilic emulsifier        is selected from the group consisting of cellulosics, gums,        polysaccharides, clays, and combinations thereof.    -   39. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 1 to 37, wherein the hydrophilic emulsifier        is hydroxyethyl cellulose.    -   40. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 1 to 39, wherein the surfactant is present in        the second aqueous phase.    -   41. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 1 to 40, wherein the surfactant is a        non-ionic surfactant.    -   42. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 1 to 41, wherein the surfactant is selected        from the group consisting of poly(vinyl alcohol), poly(acrylic        acid), poly(acrylamide), sodium caseinate, whey protein isolate        (WPI), polysaccharide, copolymers of ethylene glycol and        propylene glycol (e.g. Pluronic), polyoxyethylene derivatives of        sorbitan monolaureate (e.g. polysorbate 20, polysorbate 80) and        combinations thereof.    -   43. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 1 to 42, wherein the surfactant has a        hydrophilic/lipophilic balance (HLB) of between 10-15.    -   44. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 1 to 42, wherein the surfactant has an HLB of        about 12.    -   45. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 1 to 42, wherein the surfactant has an HLB of        about 12.3.    -   46. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 1 to 42, wherein the surfactant has an HLB of        about 13.    -   47. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 1 to 42, wherein the surfactant has an HLB of        about 13.8.    -   48. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 1 to 42, wherein the surfactant has an HLB of        about 14.    -   49. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 1 to 42, wherein the surfactant has an HLB of        about 14.4.    -   50. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 1 to 42, wherein the surfactant has an HLB of        about 15.    -   51. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 1 to 50, wherein the surfactant is an aqueous        salt solution of a styrene-maleic anhydride copolymer.    -   52. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 1 to 50, wherein the surfactant is an aqueous        salt solution of a partial ester of a styrene-maleic anhydride        copolymer.    -   53. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 1 to 52, wherein the by weight percentage (%)        does not consider the second aqueous phase.    -   54. The aqueous-in-oil-in-aqueous double emulsion composition of        any one of clauses 1 to 53 formulated as a sprayable        formulation.    -   55. The aqueous-in-oil-in-aqueous double emulsion composition of        clause 54, wherein the formulation is diluted with a solvent.    -   56. The aqueous-in-oil-in-aqueous double emulsion composition of        clause 55, wherein the solvent comprises water.    -   57. The aqueous-in-oil-in-aqueous double emulsion composition of        clause 55 or clause 56, wherein the solvent comprises sodium        caseinate (NaCSn), lactose, or a combination thereof.    -   58. A method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition, comprising:        -   (a) preparing an aqueous-in-oil emulsion composition using            an aqueous phase, an oil phase, a lipophilic emulsifier, and            an oil soluble thickener;        -   (b) combining an active ingredient into the aqueous-in-oil            emulsion composition; and        -   (c) dispersing the aqueous-in-oil emulsion composition into            a second aqueous phase.    -   59. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of clause 58, wherein the aqueous-in-oil        emulsion composition comprises an aqueous phase containing salt        (APCS).    -   60. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of clause 59, wherein the APCS comprises        water.    -   61. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of clause 60, wherein the APCS comprises        water at an amount selected from the group consisting of more        than 20% water by weight, more than 30% water by weight, more        than 50% water by weight, and more than 60% water by weight        (based on the weight of the composition).    -   62. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of any one of clauses 59 to 61, wherein the        APCS comprises one or more salts.    -   63. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of any one of clauses 59 to 62, wherein no        chloride salt is used.    -   64. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of any one of clauses 59 to 63, wherein the        salt is a non-deliquescent salt.    -   65. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of any one of clauses 59 to 64, wherein the        salt is dissolved in the aqueous phase.    -   66. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of any one of clauses 59 to 65, wherein the        salt comprises magnesium sulfate or ammonium sulfate.    -   67. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of any one of clauses 59 to 65, wherein the        salt comprises magnesium sulfate.    -   68. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of any one of clauses 59 to 65, wherein the        salt comprises ammonium sulfate.    -   69. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of any one of clauses 59 to 68, wherein the        salt comprises magnesium sulfate or ammonium sulfate the ratio        of dry weight of the salt to weight of the aqueous phase of the        aqueous-in-oil emulsion composition is at least 0.25.    -   70. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of any one of clauses 59 to 68, wherein the        salt comprises magnesium sulfate or ammonium sulfate the ratio        of dry weight of the salt to weight of the aqueous phase of the        aqueous-in-oil emulsion composition is at least 0.3.    -   71. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of any one of clauses 59 to 68, wherein the        salt comprises magnesium sulfate or ammonium sulfate the ratio        of dry weight of the salt to weight of the aqueous phase of the        aqueous-in-oil emulsion composition is at least 0.35.    -   72. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of any one of clauses 59 to 71, wherein the        ratio of the dry weight of salt to the weight of water is        selected from the group consisting of 0.05 or higher; or 0.1 or        higher; or 0.2 or higher; or 0.3 or higher; or 0.35 or higher.    -   73. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of any one of clauses 58 to 72, wherein the        active ingredient comprises a molecular complex of an        encapsulated volatile compound.    -   74. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of clause 73, wherein the composition has        the molecular complex of the encapsulated volatile compound        distributed throughout the aqueous-in-oil emulsion composition.    -   75. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of clause 73 or 74, wherein the ratio of        dry weight of the salt to dry weight of the molecular complex of        the encapsulated volatile compound is from 0.03 to 500.    -   76. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of any one of clauses 73 to 75, wherein the        molecular complex of an encapsulated volatile compound comprises        a cyclopropene molecular encapsulating agent complex.    -   77. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of clause 76, wherein the cyclopropene is        of the formula:

wherein R is a substituted or unsubstituted alkyl, alkenyl, alkynyl,cycloalkyl, cycloalkylalkyl, phenyl, or naphthyl group; wherein thesubstituents are independently halogen, alkoxy, or substituted orunsubstituted phenoxy.

-   -   78. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of clause 76, wherein the cyclopropene is        of the formula

-   -   wherein R¹ is a substituted or unsubstituted C₁-C₄ alkyl, C₂-C₄        alkenyl, C₂-C₄ alkynyl, C₃-C₆ cycloalkyl, cycloalkylalkyl,        phenyl, or napthyl group; and R², R³, and R⁴ are hydrogen.    -   79. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of clause 76, wherein the cyclopropene is        1-methylcyclopropene.    -   80. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of clause 76, wherein the molecular        encapsulating agent is alpha-cyclodextrin.    -   81. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of any one of clauses 73 to 80, wherein the        double emulsion composition comprises at least 5%, at least 10%,        at least 20%, at least 30%, at least 40%, at least 50%, or at        least 60% by weight of a complex of 1-methylcyclopropene (1-MCP)        and alpha-cyclodextrin.    -   82. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of any one of clauses 58 to 81, wherein the        oil phase comprises an oil medium.    -   83. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of clause 82, wherein the oil medium is        selected from the group consisting of soybean oil, hydrogenated        soybean oil, cotton seed oil, hydrogenated cotton seed oil,        white mineral oil, hydrotreated middle petroleum distillate,        hydrotreated light petroleum distillate, and combinations        thereof.    -   84. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of any one of clauses 58 to 83, wherein the        aqueous-in-oil emulsion composition comprises 10-20%; 20-40%;        40-60%; 15-30%; or 30-55% by weight of the oil phase.    -   85. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of any one of clauses 58 to 84, wherein the        lipophilic emulsifier is selected from the group consisting of        polyglycerol polyricinoleate, lecithin, sorbitan fatty esters,        and combinations thereof.    -   86. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of clause 85, wherein the lipophilic        emulsifier is polyglycerol polyricinoleate (PGPR).    -   87. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of any one of clauses 58 to 86, wherein the        oil soluble thickener is selected from the group consisting of        natural rubber, polypropylene, polyisoprene, polybutadiene,        poly(styrene-butadiene), poly(ethylene-propylene-diene),        polyurethane, polymethacrylate, polyisobutylene,        poly(isobutylene-succinic acid), poly(isobutylene-succinic        acid-polyacrylamide), polyurea, polyethylene, and combinations        thereof.    -   88. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of clause 87, wherein wherein the oil        soluble thickener is a (co- or homo)polymer of propylene.    -   89. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of any one of clauses 58 to 88, wherein the        second aqueous phase comprises water.    -   90. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of clause 89, water is present at a ratio        of aqueous-in-oil emulsion composition:water from 1:1 to 1:100.    -   91. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of any one of clauses 58 to 90, wherein the        method further comprises addition of a hydrophilic emulsifier to        the second aqueous phase.    -   92. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of clause 91, wherein the hydrophilic        emulsifier is selected from the group consisting of cellulosics,        gums, polysaccharides, clays, and combinations thereof.    -   93. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of clause 91, wherein the hydrophilic        emulsifier is hydroxyethyl cellulose.    -   94. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of any one of clauses 58 to 93, wherein the        method further comprises addition of a surfactant to the second        aqueous phase.    -   95. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of clause 94, wherein the surfactant is a        non-ionic surfactant.    -   96. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of clause 94, wherein the surfactant is        selected from the group consisting of poly(vinyl alcohol),        poly(acrylic acid), poly(acrylamide), sodium caseinate, whey        protein isolate (WPI), polysaccharide, copolymers of ethylene        glycol and propylene glycol (e.g. Pluronic), polyoxyethylene        derivatives of sorbitan monolaureate (e.g. polysorbate 20,        polysorbate 80) and combinations thereof.    -   97. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of any one of clauses 94 to 96, wherein the        surfactant has a hydrophilic/lipophilic balance (HLB) of between        10-15.    -   98. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of any one of clauses 94 to 96, wherein the        surfactant has an HLB of about 12.    -   99. The method for preparing an aqueous-in-oil-in-aqueous double        emulsion composition of any one of clauses 94 to 96, wherein the        surfactant has an HLB of about 12.3.    -   100. The method for preparing an aqueous-in-oil-in-aqueous        double emulsion composition of any one of clauses 94 to 96,        wherein the surfactant has an HLB of about 13.    -   101. The method for preparing an aqueous-in-oil-in-aqueous        double emulsion composition of any one of clauses 94 to 96,        wherein the surfactant has an HLB of about 13.8.    -   102. The method for preparing an aqueous-in-oil-in-aqueous        double emulsion composition of any one of clauses 94 to 96,        wherein the surfactant has an HLB of about 14.    -   103. The method for preparing an aqueous-in-oil-in-aqueous        double emulsion composition of any one of clauses 94 to 96,        wherein the surfactant has an HLB of about 14.4.    -   104. The method for preparing an aqueous-in-oil-in-aqueous        double emulsion composition of any one of clauses 94 to 96,        wherein the surfactant has an HLB of about 15.    -   105. The method for preparing an aqueous-in-oil-in-aqueous        double emulsion composition of any one of clauses 94 to 104,        wherein the surfactant is an aqueous salt solution of a        styrene-maleic anhydride copolymer.    -   106. The method for preparing an aqueous-in-oil-in-aqueous        double emulsion composition of any one of clauses 94 to 104,        wherein the surfactant is an aqueous salt solution of a partial        ester of a styrene-maleic anhydride copolymer.    -   107. The method for preparing an aqueous-in-oil-in-aqueous        double emulsion composition of any one of clauses 58 to 106,        wherein the by weight % does not consider the second aqueous        phase.    -   108. A method of treating plants or plant parts comprising the        step of contacting the plant or plant parts with the        aqueous-in-oil-in-aqueous double emulsion of any one of clauses        1 to 57.

In one aspect, an aqueous-in-oil-in-aqueous double emulsion compositionis provided. The aqueous-in-oil-in-aqueous double emulsion compositioncomprises (a) an aqueous-in-oil emulsion composition; (b) a hydrophilicemulsifier; (c) a surfactant; and (d) a second aqueous phase.

In another aspect, a method for preparing an aqueous-in-oil-in-aqueousdouble emulsion composition is provided. The method comprises (a)preparing an aqueous-in-oil emulsion composition using an aqueous phase,an oil phase, a lipophilic emulsifier, and an oil soluble thickener; (b)combining an active ingredient into the aqueous-in-oil emulsioncomposition; and (c) dispersing the aqueous-in-oil emulsion compositioninto a second aqueous phase.

In yet another aspect, a method of treating plants or plant parts isprovided. The method of treating plants or plant parts comprises thestep of contacting the plant or plant parts with anaqueous-in-oil-in-aqueous double emulsion as described herein.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 shows a schematic of the primary water-in-oil (W/O) emulsiondisclosed and the water-in-oil-in-water (W/O/W) double emulsiondisclosed herein.

DETAILED DESCRIPTION

As used herein, the phrase “stable” refer to cyclopropene content atambient temperature over time, for example after one (1) year, in asolution with no more than 15% loss as compared to day zero (0).Alternatively, the solution may be tested at 54° C. with no more than15% loss over a period of time, for example one week or four weeks. Whenthe cyclopropene content is maintained over a period of time, thesolution is a “stable” cyclopropene formulation or cyclopropenesolution.

In one embodiment, the cyclopropene content of the composition providedis stable over a period of at least ten (10), twenty (20), thirty (30),or sixty (60) days. In another embodiment, the cyclopropene content ofthe composition is stable over a period of one month, two months, threemonths, six months, or twelve months. In another embodiment, thecyclopropene content of the composition is stable over a period of oneyear, two years, or three years.

A water-in-oil-in-water type (W/O/W) double emulsion is a compartmentedstructure consisting of small aqueous droplets embedded within largeroil droplets, which themselves are dispersed within an external aqueousphase. The double emulsion composition may have at least one of thefollowing advantages: (a) high capacity of entrapment of hydrophiliccompounds; (b) ability to introduce incompatible substances into thesame system; (c) performance improvement of active compounds; and (d)protection and sustained release of chemical substances initiallyentrapped in the internal droplets.

Cyclopropene compositions comprising water and salt have been describedin U.S. Pat. No. 8,691,728, the content of which is thereby incorporatedby reference in its entirety.

When a compound is described herein as being present as a gas in anatmosphere at a certain concentration using the unit “ppm,” theconcentration is given as parts by volume of that compound per millionparts by volume of the atmosphere. Similarly, “ppb” denotes parts byvolume of that compound per billion parts by volume of the atmosphere.

The practice of the present disclosure optionally involves the use ofone or more cyclopropene compound. As used herein, a cyclopropenecompound is any compound with the formula

where each R¹, R², R³ and R⁴ is independently selected from the groupconsisting of H and a chemical group of the formula:

-(L)_(n)-Z

where n is an integer from 0 to 12. Each L is a bivalent radical.Suitable L groups include, for example, radicals containing one or moreatoms selected from B, C, N, O, P, S, Si, or mixtures thereof. The atomswithin an L group may be connected to each other by single bonds, doublebonds, triple bonds, or mixtures thereof. Each L group may be linear,branched, cyclic, or a combination thereof. In any one R group (i.e.,any one of R¹, R², R³ and R⁴) the total number of heteroatoms (i.e.,atoms that are neither H nor C) is from 0 to 6. Independently, in anyone R group the total number of non-hydrogen atoms is 50 or less. Each Zis a monovalent radical. Each Z is independently selected from the groupconsisting of a C₁-C₈ alkyl, hydrogen, halo, cyano, nitro, nitroso,azido, chlorate, bromate, iodate, isocyanato, isocyanido,isothiocyanato, pentafluorothio, and a chemical group G, wherein G is a3- to 14-membered ring system.

The R¹, R², R³, and R⁴ groups are independently selected from thesuitable groups. Among the groups that are suitable for use as one ormore of R¹, R², R³, and R⁴ are, for example, aliphatic groups,aliphatic-oxy groups, alkylphosphonato groups, cycloaliphatic groups,cycloalkylsulfonyl groups, cycloalkylamino groups, heterocyclic groups,aryl groups, heteroaryl groups, halogens, silyl groups, and mixtures andcombinations thereof. Groups that are suitable for use as one or more ofR¹, R², R³, and R⁴ may be substituted or unsubstituted.

Among the suitable R¹, R², R³, and R⁴ groups are, for example, aliphaticgroups. Some suitable aliphatic groups include, for example, alkyl,alkenyl, and alkynyl groups. Suitable aliphatic groups may be linear,branched, cyclic, or a combination thereof. Independently, suitablealiphatic groups may be substituted or unsubstituted.

As used herein, a chemical group of interest is said to be “substituted”if one or more hydrogen atoms of the chemical group of interest isreplaced by a substituent.

Also among the suitable R¹, R², R³, and R⁴ groups are, for example,substituted and unsubstituted heterocyclyl groups that are connected tothe cyclopropene compound through an intervening oxy group, amino group,carbonyl group, or sulfonyl group; examples of such R¹, R², R³, and R⁴groups are heterocyclyloxy, heterocyclylcarbonyl, diheterocyclylamino,and diheterocyclylaminosulfonyl.

Also among the suitable R¹, R², R³, and R⁴ groups are, for example,substituted and unsubstituted heterocyclic groups that are connected tothe cyclopropene compound through an intervening oxy group, amino group,carbonyl group, sulfonyl group, thioalkyl group, or aminosulfonyl group;examples of such R¹, R², R³, and R⁴ groups are diheteroarylamino,heteroarylthioalkyl, and diheteroarylaminosulfonyl.

Also among the suitable R¹, R², R³, and R⁴ groups are, for example,hydrogen, fluoro, chloro, bromo, iodo, cyano, nitro, nitroso, azido,chlorate, bromate, iodate, isocyanato, isocyanido, isothiocyanato,pentafluorothio, acetoxy, carboethoxy, cyanato, nitrato, nitrito,perchlorato, allenyl, butylmercapto, diethylphosphonato,dimethylphenylsilyl, isoquinolyl, mercapto, naphthyl, phenoxy, phenyl,piperidino, pyridyl, quinolyl, triethylsilyl, trimethylsilyl, andsubstituted analogs thereof.

As used herein, the chemical group G is a 3- to 14-membered ring system.Ring systems suitable as chemical group G may be substituted orunsubstituted; they may be aromatic (including, for example, phenyl andnapthyl) or aliphatic (including unsaturated aliphatic, partiallysaturated aliphatic, or saturated aliphatic); and they may becarbocyclic or heterocyclic. Among heterocyclic G groups, some suitableheteroatoms are, for example, nitrogen, sulfur, oxygen, and combinationsthereof. Ring systems suitable as chemical group G may be monocyclic,bicyclic, tricyclic, polycyclic, spiro, or fused; among suitablechemical group G ring systems that are bicyclic, tricyclic, or fused,the various rings in a single chemical group G may be all the same typeor may be of two or more types (for example, an aromatic ring may befused with an aliphatic ring).

In one embodiment, one or more of R¹, R², R³, and R⁴ is hydrogen orC₁-C₁₀ alkyl. In another embodiment, each of R¹, R², R³, and R⁴ ishydrogen or a C₁-C₈ alkyl. In another embodiment, each of R¹, R², R³,and R⁴ is hydrogen or C₁-C₄ alkyl. In another embodiment, each of R¹,R², R³, and R⁴ is hydrogen or methyl. In another embodiment, R¹ is C₁-C₄alkyl and each of R², R³, and R⁴ is hydrogen. In another embodiment, R¹is methyl and each of R², R³, and R⁴ is hydrogen, and the cyclopropenecompound is known herein as 1-methylcyclopropene or “1-MCP.”

Various embodiments of the invention are described herein as follows. Inone aspect of the present disclosure, an aqueous-in-oil-in-aqueousdouble emulsion composition is provided. The aqueous-in-oil-in-aqueousdouble emulsion composition comprises (a) an aqueous-in-oil emulsioncomposition; (b) a hydrophilic emulsifier; (c) a surfactant; and (d) asecond aqueous phase. In certain embodiments, the aqueous-in-oilemulsion composition comprises an aqueous phase containing salt (APCS).In some embodiments, the APCS comprises water. In certain embodiments,the APCS contains more than 20% water by weight, based on the weight ofthe composition. Some embodiments have water in an amount, by weightbased on the weight of the composition, of 30% or more; 50% or more; or60% or more.

Also contemplated are embodiments in which the composition of thepresent invention is present in a formulation that contains more than30% by weight, based on the weight of the formulation, a liquid thatcontains at least one compound other than water. Such a liquid may haveno water. In some embodiments, such a liquid may be a mixture of waterand one or more water miscible liquids other than water. In such amixture, the amount of water, by weight based on the weight of theliquid, may be 99% or less; or 95% or less; 90% or less; or 50% or less;or 10% or less. Independently, in such a mixture, the amount of water,by weight based on the weight of the liquid, may be 5% or more; or 45%or more; or 75% or more.

In certain embodiments, the APCS comprises one or more salts. As usedherein, a salt is an ionic compound comprising at least one anion and atleast one cation. A salt may be present as an ionic solid or as asolution in water. Some suitable anions are, for example, the anionresidues of acids that have pKa values of 5 or lower. Some suitablesalts, for example, are compounds that, regardless of the method used toactually make them, have the structure of a compound that would beformed by substituting a cation that is not a hydrogen ion for thehydrogen ion in an acid that has a pKa of 5 or lower; an acid that has apKa of 2.5 or lower; or an acid that has a pKa of 1.0 or lower.

In some embodiments, one or more salt is used that is suitable fortreating agricultural plants. Independently, in some embodiments, one ormore salt is used that has solubility in water at 25° C. at 1 atmospherepressure, per 100 mL of water, of 1 gram or more, or 3 grams or more, or10 grams or more, or 20 grams or more, or 30 grams or more.

Some non-limiting examples of suitable anions are these: acetate,chloride, nitrate, phosphate, or sulfate. Independently, somenon-limiting examples of suitable cations are these: ammonium, calcium,magnesium, manganese, potassium, or sodium. It is contemplated thatsuitable cations and suitable anions may be used in any combination ormixture, with the provision that at least one salt is used that is notcalcium chloride.

In some embodiments, no appreciable amount of calcium chloride ispresent in the composition of the present invention. It is contemplatedthat a finite but non-appreciable amount of calcium chloride may bepresent in a composition of the present invention (for example, becauseof one or more impurities). Calcium chloride may be present with a ratioof dry weight of calcium chloride to dry weight of total salt of 0.03 orless; or 0.01 or less; or 0.003 or less; or 0.001 or less; or zero.

In some embodiments, one or more salt is used that is selected fromammonium acetate, ammonium chloride, ammonium nitrate, ammoniumphosphate, ammonium sulfate, calcium acetate, magnesium acetate,magnesium chloride, magnesium sulfate, manganese nitrate, potassiumacetate, potassium chloride, potassium phosphate, potassium sulfate,sodium acetate, sodium chloride, sodium phosphate, or sodium sulfate. Insome embodiments, one or more salt is used that is selected fromammonium acetate, ammonium chloride, ammonium sulfate, magnesiumacetate, magnesium chloride, magnesium sulfate, potassium acetate,potassium chloride, potassium phosphate, sodium acetate, sodiumchloride, disodium phosphate, or sodium sulfate. In some embodiments,one or more salt is used that is selected from ammonium chloride,ammonium sulfate, magnesium sulfate, sodium acetate, sodium chloride,disodium phosphate, or sodium sulfate. Mixtures of suitable salts arealso suitable. In one embodiment, the salt comprises magnesium sulfateor ammonium sulfate.

In some embodiments, one or more sulfate salt is used. Independently, insome embodiments, no chloride salt is used.

In the practice of the present invention, some embodiments of thepresent invention contain at least one non-deliquescent salt. Anon-deliquescent salt is a salt that is not a deliquescent salt. Adeliquescent salt is a salt that, in its solid form, readily absorbslarge amounts of water from the atmosphere. At 25° C. and 1 atmospherepressure, if relative humidity is not zero, a deliquescent salt willabsorb sufficient water from the atmosphere to form a liquid solution.Some known deliquescent salts are, for example, ammonium formate;calcium chloride; magnesium chloride; potassium phosphate, monobasic;and potassium phosphate, dibasic. Some embodiments of the presentinvention do not contain appreciable amounts of any deliquescent salt.It is contemplated that a finite but non-appreciable amount ofdeliquescent salt may be present in a embodiment of the presentinvention (for example, because of one or more impurities). Deliquescentsalt may be present in a ratio of dry weight of deliquescent salt to dryweight of total salt of 0.01 or lower; or 0.001 or lower; or zero.

In some embodiments, the ratio of the weight of salt to the weight ofcyclopropene molecular encapsulating agent complex is 0.01 or greater;or 0.03 or greater; or 0.1 or greater; or 0.3 or greater; or 1 orgreater. Independently, in some embodiments, the ratio of the weight ofsalt to the weight of cyclopropene molecular encapsulating agent complexis 200 or less; or 100 or less; or 50 or less; or 20 or less.

In yet another aspect, the salt is dissolved in the aqueous phase. Incertain embodiments, the salt comprises magnesium sulfate or ammoniumsulfate. In other embodiments, the salt comprises magnesium sulfate. Inyet other embodiments, the salt comprises ammonium sulfate.

In compositions of the present invention, the ratio of the dry weight ofsalt to the dry weight of cyclopropene molecular encapsulating agentcomplex is 0.03 or higher; or 0.1 or higher; or 0.3 or higher; or 1 orhigher. Independently, in compositions of the present invention, theratio of the dry weight of salt to the dry weight of cyclopropenemolecular encapsulating agent complex is 500 or lower; or 200 or lower;or 100 or lower; or 50 or lower; or 20 or lower.

In some embodiments, the composition of the present invention containsmore than 20% water by weight, based on the weight of the composition.Some embodiments have water in an amount, by weight based on the weightof the composition, of 30% or more; 50% or more; or 60% or more.

In some embodiments, the ratio of the dry weight of salt to the weightof water is 0.05 or higher; or 0.1 or higher; or 0.2 or higher; or 0.3or higher; or 0.35 or higher. In one embodiment, the salt comprisesmagnesium sulfate or ammonium sulfate the ratio of dry weight of thesalt to weight of the aqueous phase of the aqueous-in-oil emulsioncomposition is at least 0.25. In another embodiment, the salt comprisesmagnesium sulfate or ammonium sulfate the ratio of dry weight of thesalt to weight of the aqueous phase of the aqueous-in-oil emulsioncomposition is at least 0.3. In yet another embodiment, the saltcomprises magnesium sulfate or ammonium sulfate the ratio of dry weightof the salt to weight of the aqueous phase of the aqueous-in-oilemulsion composition is at least 0.35. In some embodiments, the ratio ofthe dry weight of salt to the weight of water is selected from the groupconsisting of 0.05 or higher; or 0.1 or higher; or 0.2 or higher; or 0.3or higher; or 0.35 or higher.

Independently, in some embodiments, the ratio of the dry weight of saltto the weight of water is 0.6 or lower; or 0.5 or lower.

In some embodiments, the ratio of the dry weight of cyclopropenemolecular encapsulating complex to the sum of the weight of water andthe weight of salt is 0.005 or higher; or 0.01 or higher; or 0.02 orhigher; or 0.05 or higher; or 0.1 or higher; or 0.2 or higher.Independently, in some embodiments, the ratio of the dry weight ofcyclopropene molecular encapsulating complex to the sum of the weight ofwater and the weight of salt is 0.65 or lower; or 0.45 or lower; or 0.3or lower.

In some embodiments, at least one cyclopropene molecular encapsulatingcomplex is distributed throughout the water. Independently, in someembodiments, at least one salt is dissolved in the water.

In some embodiments, the ratio of the dry weight of salt to the weightof water is selected from the group consisting of 0.05 or higher; or 0.1or higher; or 0.2 or higher; or 0.3 or higher; or 0.35 or higher.

In one embodiment, the active ingredient is dispersed in the aqueousphrase. In another embodiment, the active ingredient comprises amolecular complex of an encapsulated volatile compound. In anotherembodiment, the ratio of dry weight of the salt to weight of the firstaqueous phase is at least 0.25; at least 0.3; or at least 0.35.

In certain aspects, the APCS comprises an active ingredient. In someembodiments, the active ingredient comprises a molecular complex of anencapsulated volatile compound. In certain embodiments, the compositionhas the molecular complex of the encapsulated volatile compounddistributed throughout the aqueous-in-oil emulsion composition. In someaspects, the ratio of dry weight of the salt to dry weight of themolecular complex of the encapsulated volatile compound is from 0.03 to500.

In some embodiments, the molecular complex of an encapsulated volatilecompound comprises a cyclopropene molecular encapsulating agent complex.In certain aspects, molecular complex of the encapsulated volatilecompound is distributed throughout the aqueous phase. In some aspects,the cyclopropene is of the formula:

wherein R is a substituted or unsubstituted alkyl, alkenyl, alkynyl,cycloalkyl, cycloalkylalkyl, phenyl, or naphthyl group; wherein thesubstituents are independently halogen, alkoxy, or substituted orunsubstituted phenoxy. In one embodiment, R is a C₁-C₈ alkyl. In anotherembodiment, R is methyl.

In other embodiments, the cyclopropene is of the formula:

wherein R¹ is a substituted or unsubstituted C₁-C₄ alkyl, C₂-C₄ alkenyl,C₂-C₄ alkynyl, C₃-C₆ cycloalkyl, cycloalkylalkyl, phenyl, or napthylgroup; and R², R³, and R⁴ are hydrogen.

In certain aspects, the cyclopropene is 1-methylcyclopropene (1-MCP). Inanother embodiment, the molecular encapsulating agent is selected fromthe group consisting of substituted cyclodextrins, unsubstitutedcyclodextrins, and combinations thereof. In a further embodiment, themolecular encapsulating agent comprises alpha-cyclodextrin.

In one embodiment, the solid particles comprise at least 5%, at least10%, at least 20%, at least 30%, at least 40%, at least 50%, or at least60% by weight of the composition. In another embodiment, the solidparticles comprise 10-20%, 10-30%, 10-40%, 10-50%, 10-60%, 20-40%,30-60%, or 40-60% by weight of the composition. In another embodiment,the composition comprises at least 5%, at least 10%, at least 20%, atleast 30%, at least 40%, at least 50%, or at least 60% by weight of acomplex of 1-methylcyclopropene (1-MCP) and alpha-cyclodextrin. Inanother embodiment, the composition comprises 10-20%, 10-30%, 10-40%,10-50%, 10-60%, 20-40%, 30-60%, or 40-60% by weight of a complex of1-methylcyclopropene (1-MCP) and alpha-cyclodextrin.

When a cyclopropene compound is used, in some embodiments theconcentration of the cyclopropene compound in the atmosphere is 0.5 ppbor higher; 1 ppb or higher; 10 ppb or higher; or 100 ppb or higher. Insome embodiments, the concentration of the cyclopropene compound is 100ppm or lower, 50 ppm or lower, 10 ppm or lower, or 5 ppm or lower.

In some embodiments, a cyclopropene is used that has boiling point atone atmosphere pressure of 50° C. or lower; 25° C. or lower; or 15° C.or lower. Independently, in some embodiments, a cyclopropene is usedthat has boiling point at one atmosphere pressure of −100° C. or higher;−50° C. or higher; −25° C. or higher; or 0° C. or higher.

The cyclopropenes applicable to this invention may be prepared by anymethod. Some suitable methods of preparation of cyclopropenes are theprocesses disclosed in U.S. Pat. Nos. 5,518,988 and 6,017,849.

In some embodiments, at least one molecular encapsulating agent is usedto encapsulate at least one volatile compound. In some embodiments, atleast one molecular encapsulating agent encapsulates one or morecyclopropene or a portion of one or more cyclopropene. A complex thatcontains a cyclopropene molecule or a portion of a cyclopropene moleculeencapsulated in a molecule of a molecular encapsulating agent is knownherein as a “cyclopropene molecular encapsulating agent complex.”

In some embodiments, at least one cyclopropene molecular encapsulatingagent complex forms an inclusion complex. In such an inclusion complex,the molecular encapsulating agent forms a cavity, and the cyclopropeneor a portion of the cyclopropene is located within that cavity. In someof such inclusion complexes, there is no covalent bonding between thecyclopropene and the molecular encapsulating agent. Independently, insome of such inclusion complexes, there is no ionic bonding between thecyclopropene and the molecular encapsulating complex, whether or notthere is any electrostatic attraction between one or more polar moietyin the cyclopropene and one or more polar moiety in the molecularencapsulating agent.

In some embodiments of the inclusion complexes, the interior of thecavity of the molecular encapsulating agent is substantially apolar orhydrophobic or both, and the cyclopropene (or the portion of thecyclopropene located within that cavity) is also substantially apolar orhydrophobic or both. While the present invention is not limited to anyparticular theory or mechanism, it is contemplated that, in such apolarcyclopropene molecular encapsulating agent complexes, van der Waalsforces, or hydrophobic interactions, or both, cause the cyclopropenemolecule or portion thereof to remain within the cavity of the molecularencapsulating agent.

The cyclopropene molecular encapsulation agent complexes can be preparedby various means. For one example, such complexes are prepared bycontacting the cyclopropene with a solution or slurry of the molecularencapsulation agent and then isolating the complex, using processesdisclosed in U.S. Pat. No. 6,017,849. For another example, in one methodof making a complex in which 1-MCP is encapsulated in a molecularencapsulating agent, the 1-MCP gas is bubbled through a solution ofalpha-cyclodextrin in water, from which the complex first precipitatesand is then isolated by filtration. In some embodiments, complexes aremade by the above method and, after isolation, are dried and stored insolid form, for example as a powder, for later addition to usefulcompositions.

The amount of molecular encapsulating agent can usefully becharacterized by the ratio of moles of molecular encapsulating agent tomoles of cyclopropene. In some embodiments, the ratio of moles ofmolecular encapsulating agent to moles of cyclopropene is 0.1 or larger;0.2 or larger; 0.5 or larger; or 0.9 or larger. In some embodiments, theratio of moles of molecular encapsulating agent to moles of cyclopropeneis 2.0 or lower; 1.5 or lower; or 1.0 or lower.

Suitable molecular encapsulating agents include, for example, organicand inorganic molecular encapsulating agents. Suitable organic molecularencapsulating agents include, for example, substituted cyclodextrins,unsubstituted cyclodextrins, and crown ethers. Suitable inorganicmolecular encapsulating agents include, for example, zeolites. Mixturesof suitable molecular encapsulating agents are also suitable. In someembodiments of the invention, the encapsulating agent isalpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, or a mixturethereof. In some embodiments of the invention, alpha-cyclodextrin isused. The preferred encapsulating agent will vary depending upon thestructure of the cyclopropene or cyclopropenes being used. A particularcyclodextrin or mixture of cyclodextrins, cyclodextrin polymers,modified cyclodextrins, or mixtures thereof can also be used.

In some aspects, the aqueous-in-oil emulsion composition comprises anoil phase comprising an oil medium. In some embodiments, the oil mediumis selected from the group consisting of soybean oil, hydrogenatedsoybean oil, cotton seed oil, hydrogenated cotton seed oil, whitemineral oil, hydrotreated middle petroleum distillate, hydrotreatedlight petroleum distillate, and combinations thereof. In a furtherembodiment, the white mineral oil comprises Blandol and/or Klearol. Inanother further embodiment, the hydrotreated middle petroleum distillatecomprises Conosol 260, Unipar SH 260 CC, and/or Isopar V. In anotherfurther embodiment, the hydrotreated light petroleum distillatecomprises Unipar SH 210 AS and/or Isopar M. In another embodiment, thelipophilic emulsifier or hydrophobic emulsifier is selected from thegroup consisting of polyglycerol polyricinoleate, lecithin, sorbitanfatty esters (e.g., Span 80), and combinations thereof. In anotherembodiment, the oil soluble thickener or hydrophilic emulsifier isselected from the group consisting of natural rubber, polypropylene,polyisoprene, polybutadiene, poly(styrene-butadiene),poly(ethylene-propylene-diene), polyurethane, polymethacrylate,polyisobutylene, poly(isobutylene-succinic acid),poly(isobutylene-succinic acid-polyacrylamide), polyurea, polyethylene,and combinations thereof. In a further embodiment, the polymericthickener comprises a higher molecular weight component and a lowermolecular weight component, characterized in that the thickenercomprises a mixture of (1) a (co- or homo)polymer of propylene with aweight average molecular weight of more than 200,000 and (2) a (co- orhomo)polymer of propylene with a weight average molecular weight of lessthan 200,000. In another embodiment, the oil soluble thickener orhydrophilic emulsifier is selected from the group consisting ofpoly(vinyl alcohol), poly(acrylic acid), poly(acrylamide), sodiumcaseinate, whey protein isolate (WPI), polysaccharide, and combinationsthereof.

In another embodiment, the polymeric thickener comprises a highmolecular component comprising a (co- or homo)polymer of propylene witha weight average molecular weight of at least 200,000 or200,000-350,000, and low molecular component comprising a (co- orhomo)polymer of propylene with a weight average molecular weight of lessthan 100,00 or 50,000-100,000. The weight ratio between the highmolecular weight component and the low molecular weight component in thepolymeric thickener can be between 1:40 and 3:1; between 1:40 and 1:1;between 1:40 and 1:5; between 1:25 and 1:15; or between 1:18 and 1:20.

In a further embodiment, the low molecular weight component comprises apolypropylene copolymer or a polypropylene homopolymer with a melt flowrate of 500-1500 dg/min, or 750-1250 dg/min. as determined by test ASTMD-1238. In another embodiment, the high molecular weight component has amelt flow rate (ASTM D-1238) of 1.5-15; 1.5-7; or 3-5 dg/min. In afurther or alternative embodiment, the high molecular weight componentcomprises a polypropylene homopolymer or a propylene/ethylene-copolymer.

In another embodiment, the composition comprises 5-10%; 10-20%; or 8-15%by weight of an active ingredient. In another embodiment, thecomposition comprises 10-20%; 20-40%; 40-60%; 15-30%; 20-60%; or 30-60%by weight of the first aqueous phase comprising at least onenon-deliquescent salt. In another embodiment, the composition comprises10-20%; 20-40%; 40-60%; 15-30%; 20-60%; or 30-60% by weight of an oilphase comprising an oil medium. In another embodiment, the compositioncomprises 0.1-2%; 2-5%; 5-10%; 10-20%; or 7-15% by weight of alipophilic emulsifier or hydrophobic emulsifier. In another embodiment,the composition comprises 0.1-2%; 2-5%; 1-3%; or 1.5-4% by weight of anoil soluble thickener or a hydrophilic emulsifier.

In certain embodiments, the aqueous-in-oil emulsion compositioncomprises a lipophilic emulsifier. In some embodiments, the lipophilicemulsifier is selected from the group consisting of polyglycerolpolyricinoleate, lecithin, sorbitan fatty esters, and combinationsthereof. In one embodiment, the lipophilic emulsifier is polyglycerolpolyricinoleate (PGPR).

In certain embodiments, the aqueous-in-oil emulsion compositioncomprises an oil soluble thickener. In some embodiments, the oil solublethickener is selected from the group consisting of natural rubber,polypropylene, polyisoprene, polybutadiene, poly(styrene-butadiene),poly(ethylene-propylene-diene), polyurethane, polymethacrylate,polyisobutylene, poly(isobutylene-succinic acid),poly(isobutylene-succinic acid-polyacrylamide), polyurea, polyethylene,and combinations thereof. In one embodiment, the oil soluble thickeneris a (co- or homo)polymer of propylene.

In certain aspects, the second aqueous phase comprises water. In someembodiments, water is present at a ratio of aqueous-in-oil emulsioncomposition:water from 1:1 to 1:100.

In some aspects, the hydrophilic emulsifier is present in the secondaqueous phase. In some embodiments, the hydrophilic emulsifier isselected from the group consisting of cellulosics (e.g., hydroxyethylcellulose), gums (e.g., guar, xanthan), polysaccharides (e.g.,carragenaan), clays (e.g., bentonite, and other montmorillonite clays),and combinations thereof. In one embodiment, the hydrophilic emulsifieris hydroxyethyl cellulose.

In some aspects, the surfactant is present in the second aqueous phase.In some embodiments, the surfactant is a non-ionic surfactant. In someembodiments, the surfactant is selected from the group consisting ofpoly(vinyl alcohol), poly(acrylic acid), poly(acrylamide), sodiumcaseinate, whey protein isolate (WPI), polysaccharide, copolymers ofethylene glycol and propylene glycol (e.g. Pluronic), polyoxyethylenederivatives of sorbitan monolaureate (e.g. polysorbate 20, polysorbate80) and combinations thereof.

In some embodiments, the surfactant has a hydrophilic/lipophilic balance(HLB) of between 10-15. In other embodiments, the surfactant has an HLBof about 12. In yet other embodiments, the surfactant has an HLB ofabout 12.3. In some embodiments, the surfactant has an HLB of about 13.In other embodiments, the surfactant has an HLB of about 13.8. In yetother embodiments, the surfactant has an HLB of about 14. In someembodiments, the surfactant has an HLB of about 14.4. the surfactant hasan HLB of about 15.

In certain aspects, the surfactant is an aqueous salt solution of astyrene-maleic anhydride copolymer. In other aspects, the surfactant isan aqueous salt solution of a partial ester of a styrene-maleicanhydride copolymer.

In a further embodiment, the surfactant is selected from the groupconsisting of fatty ethoxylates, fatty acid esters of polyhydroxycompounds, amide oxides, alkyl oxide block copolymers, silicone basednonionic surfactants, fluoro-surfactants, and combinations thereof.

In some embodiments, one or more cationic surfactant is used. Suitablecationic surfactants include, for example, amine surfactants andquaternary ammonium salt surfactants. In some embodiments, no cationicsurfactant is used.

In some embodiments, one or more nonionic surfactant is used. Amongembodiments in which one or more nonionic surfactant is used, somesuitable nonionic surfactants include, for example, fatty ethoxylates,fatty acid esters of polyhydroxy compounds, amide oxides, alkyl oxideblock copolymers, silicone based nonionic surfactants,fluorosurfactants, and mixtures thereof.

Suitable fatty ethoxylates include, for example, ethoxylates of fattyalcohols, ethoxylates of fatty acids, ethoxylates of fattyethanolamides, and ethoxylates of fatty amines. Suitable ethoxylates offatty alcohols include, for example, ethoxylates of fatty alcohols thathave any combination of the following characteristics: linear orbranched; primary or secondary; alkyl or alkyl aryl. In someembodiments, one or more fatty ethoxylate is used that is an aryl alkylethoxylate, a fatty alcohol ethoxylate, or a mixture thereof.

Suitable silicone based nonionic surfactants include, for example, thosewith the formula

where n is 1 to 5, m is 0 to 4, and Q is

where p is 1 to 6, and q is 3 to 20. In some embodiments, n is 1.Independently, in some embodiments, m is zero. Independently, in someembodiments, p is 3. Independently, in some embodiments, q is 7 or 8 ora mixture thereof. One further example of a suitable nonionic surfactantis Atplus 595. Mixtures of suitable surfactants are also suitable

In various embodiments, by weight percentage (%) recited herein does notconsider the second aqueous phase.

In some embodiments, no composition of the present invention includesone or more metal-complexing agents.

In some embodiments, one or more compositions of the present inventionincludes one or more metal-complexing agents. A metal-complexing agentis a compound that is capable of forming coordinate bonds with metalatoms. Some metal-complexing agents are chelating agents. As usedherein, a “chelating agent” is a compound, each molecule of which iscapable of forming two or more coordinate bonds with a single metalatom. Some metal-complexing agents form coordinate bonds with metalatoms because the metal-complexing agents contain electron-donor atomsthat participate in coordinate bonds with metal atoms. Suitablechelating agents include, for example, organic and inorganic chelatingagents. Among the suitable inorganic chelating agents are, for example,phosphorous-containing chelating agents such as, for example,tetrasodium pyrophosphate, sodium tripolyphosphate, andhexametaphosphoric acid. Among the suitable organic chelating agents arethose with macrocyclic structures and non-macrocyclic structures. Amongthe suitable macrocyclic organic chelating agents are, for example,porphine compounds, cyclic polyethers (also called crown ethers), andmacrocyclic compounds with both nitrogen and oxygen atoms.

Some suitable organic chelating agents that have non-macrocyclicstructures are, for example, aminocarboxylic acids, 1,3-diketones,hydroxycarboxylic acids, polyamines, aminoalcohols, aromaticheterocyclic bases, phenol, aminophenols, oximes, Shiff bases, sulfurcompounds, and mixtures thereof. In some embodiments, the chelatingagent includes one or more aminocarboxylic acids, one or morehydroxycarboxylic acids, one or more oximes, or a mixture thereof. Somesuitable aminocarboxylic acids include, for example,ethylenediaminetetraacetic acid (EDTA),hydroxyethylethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid(NTA), N-dihydroxyethylglycine (2-HxG),ethylenebis(hydroxyphenylglycine) (EHPG), and mixtures thereof. Somesuitable hydroxycarboxylic acids include, for example, tartaric acid,citric acid, gluconic acid, 5-sulfosalicylic acid, and mixtures thereof.Some suitable oximes include, for example, dimethylglyoxime,salicylaldoxime, and mixtures thereof. In some embodiments, EDTA isused.

Some additional suitable chelating agents are polymeric. Some suitablepolymeric chelating agents include, for example, polyethyleneimines,polymethacryloylacetones, poly(acrylic acid), and poly(methacrylicacid). Poly(acrylic acid) is used in some embodiments.

Some suitable metal-complexing agents that are not chelating agents are,for example, alkaline carbonates, such as, for example, sodiumcarbonate.

Metal-complexing agents may be present in neutral form or in the form ofone or more salts. Mixtures of suitable metal-complexing agents are alsosuitable.

In some embodiments, the amount of metal-complexing agent is, based onthe total weight of the water, 25% by weight or less; or 10% by weightor less; or 1% by weight or less. Independently, in some embodiments,the amount of metal-complexing agent is, based on the total weight ofthe water, 0.00001% or more; or 0.0001% or more; or 0.01% or more.

Independently, in some embodiments, the molar concentration ofmetal-complexing agent in the water (i.e., moles of metal-complexingagent per liter of water) is 0.00001 mM (i.e., milli-molar) or greater;or 0.0001 mM or greater; or 0.001 mM or greater; or 0.01 mM or greater;or 0.1 mM or greater. Independently, in some embodiments, theconcentration of metal-complexing agent is 100 mM or less; or 10 mM orless; or 1 mM or less.

In some embodiments, the ratio of the weight of metal complexing agentto the weight of cyclopropene molecular encapsulating agent complex is0.001 or greater; or 0.003 or greater; or 0.01 or greater; or 0.03 orgreater; or 0.1 or greater. Independently, in some embodiments, theratio of the weight of metal complexing agent to the weight ofcyclopropene molecular encapsulating agent complex is 1000 or lower; or300 or lower; or 100 or lower; or 30 or lower; or 10 or lower.

In some embodiments of the present invention, one or more adjuvants arealso included in the composition of the present invention. The use ofadjuvants is considered optional in the practice of the presentinvention. Adjuvants may be used alone or in any combination. When morethan one adjuvant is used, it is contemplated that any combination ofone or more adjuvants may be used. Some suitable adjuvants aresurfactants, alcohols, oils, extenders, pigments, fillers, binders,plasticizers, lubricants, wetting agents, spreading agents, dispersingagents, stickers, adhesives, defoamers, thickeners, transport agents,and emulsifying agents.

In some embodiments, a composition of the present invention is used thatcontains at least one adjuvant selected from alcohols, oils, andmixtures thereof; such a composition may or may not additionally containone or more surfactant.

In some embodiments, a composition of the present invention may bestored for later use. Compositions of the present invention may bestored in any form. In some embodiments, the composition of the presentinvention may be stored in a sealed container. A sealed container is onethat is constructed so that no effective amount of material (solid,liquid, or gas) passes in or out of the container. Independent of thetype of container used, compositions of the present invention may bestored for 3 hours or longer; or 8 hours or longer; or 1 day or longer;or 1 week or longer; or 3 weeks or longer; or 2 months or longer; or 6months or longer.

In the practice of the present invention, one or more oils are used. Asused herein, an “oil” is a compound that is liquid at 25° C. and 1atmosphere pressure and that has a boiling point at 1 atmospherepressure of 30° C. or higher. As used herein, “oil” optionally does notinclude water, optionally does not include surfactants (as describedherein), and optionally does not include dispersants (as describedherein).

In some embodiments, one or more oil may be used that has boiling pointof 50° C. or higher; or 75° C. or higher; or 100° C. or higher. In someembodiments, the oil used has boiling point of 50° C. or higher. In someembodiments, the oil used has boiling point of 75° C. or higher. In someembodiments, the oil used has boiling point of 100° C. or higher.Independently, in some of the embodiments that use oil, one or more oilmay be used that has an average molecular weight of 100 or higher; or200 or higher; or 500 or higher. In some embodiments, the oil used hasan average molecular weight of 100 or higher. In some embodiments, theoil used has an average molecular weight of 200 or higher. In someembodiments, the oil used has an average molecular weight of 500 orhigher.

An oil may be either a hydrocarbon oil (i.e., an oil whose moleculecontains only atoms of carbon and hydrogen) or a non-hydrocarbon oil(i.e., an oil whose molecule contains at least at least one atom that isneither carbon nor hydrogen).

Some suitable hydrocarbon oils are, for example, straight, branched, orcyclic alkane compounds with 6 or more carbon atoms. Some other suitablehydrocarbon oils, for example, have one or more carbon-carbon doublebond, one or more carbon-carbon triple bond, or one or more aromaticring, possibly in combination with each other and/or in combination withone or more alkane group. Some suitable hydrocarbon oils are obtainedfrom petroleum distillation and contain a mixture of compounds, alongwith, in some cases, impurities. Hydrocarbon oils obtained frompetroleum distillation may contain a relatively wide mixture ofcompositions or may contain relatively pure compositions. In someembodiments, hydrocarbon oils are used that contain 6 or more carbonatoms. In some embodiments, hydrocarbon oils are used that contain 18 orfewer carbon atoms. In some embodiments, every hydrocarbon oil that isused contains 18 or fewer carbon atoms. In some embodiments, everyhydrocarbon oil that is used contains 6 or more carbon atoms. Somesuitable hydrocarbon oils include, for example, hexane, decane,dodecane, hexadecane, diesel oil, hydrotreated light petroleumdistillates, hydrotreated medium petroleum distillates, refinedparaffinic oil (e.g., Ultrafine™ spray oil from Sun Company), andmixtures thereof. In some embodiments, the oil used is a hydrocarbonoil.

Among embodiments that use non-hydrocarbon oil, some suitablenon-hydrocarbon oils are, for example, fatty non-hydrocarbon oils.“Fatty” means herein any compound that contains one or more residues offatty acid. Fatty acids are long-chain carboxylic acids, with chainlength of at least 4 carbon atoms. Typical fatty acids have chain lengthof 4 to 18 carbon atoms, though some have longer chains. Linear,branched, or cyclic aliphatic groups may be attached to the long chain.Fatty acid residues may be saturated or unsaturated, and they maycontain functional groups, including for example alkyl groups, epoxidegroups, halogens, sulfonate groups, or hydroxyl groups, which are eithernaturally occurring or that have been added. Some suitable fattynon-hydrocarbon oils are, for example, fatty acids; esters of fattyacids; amides of fatty acids; dimers, trimers, oligomers, or polymersthereof; and mixtures thereof.

Some of the suitable fatty non-hydrocarbon oils are, for example, estersof fatty acids. Such esters include, for example, glycerides of fattyacids. Glycerides are esters of fatty acids with glycerol, and they maybe mono-, di-, or triglycerides. A variety of triglycerides are found innature. Most of the naturally occurring triglycerides contain residuesof fatty acids of several different lengths and/or compositions. Somesuitable triglycerides are found in animal sources such as, for example,dairy products, animal fats, or fish. Further examples of suitabletriglycerides are oils found in plants, such as, for example, coconut,palm, cottonseed, olive, tall, peanut, safflower, sunflower, corn,soybean, linseed, tung, castor, canola, citrus seed, cocoa, oat, palm,palm kernel, rice bran, cuphea, or rapeseed oil.

Among the suitable triglycerides, independent of where they are found,are those, for example, that contain at least one fatty acid residuethat has 14 or more carbon atoms. Some suitable triglycerides have fattyacid residues that contain 50% or more by weight, based on the weight ofthe residues, fatty acid residues with 14 or more carbon atoms, or 16 ormore carbon atoms, or 18 or more carbon atoms. One example of a suitabletriglyceride is soybean oil.

Suitable fatty non-hydrocarbon oils may be synthetic or natural ormodifications of natural oils or a combination or mixture thereof. Amongsuitable modifications of natural oils are, for example, alkylation,hydrogenation, hydroxylation, alkyl hydroxylation, alcoholysis,hydrolysis, epoxidation, halogenation, sulfonation, oxidation,polymerization, and combinations thereof. In some embodiments, alkylated(including, for example, methylated and ethylated) oils are used. Onesuitable modified natural oil is methylated soybean oil.

Also among the suitable fatty non-hydrocarbon oils are self-emulsifyingesters of fatty acids.

Another group of suitable non-hydrocarbon oils is the group of siliconeoils. Silicone oil is an oligomer or polymer that has a backbone that ispartially or fully made up of —Si—O— links. Silicone oils include, forexample, polydimethylsiloxane oils. Polydimethylsiloxane oils areoligomers or polymers that contain units of the form

where at least one of the units has X1=CH₃. In other units, X1 may beany other group capable of attaching to Si, including, for example,hydrogen, hydroxyl, alkyl, alkoxy, hydroxyalkyl, hydroxyalkoxy,alkylpolyalkoxyl, substituted versions thereof, or combinations thereof.Substituents may include, for example, hydroxyl, alkoxyl, polyethoxyl,ether linkages, ester linkages, amide linkages, other substituents, orany combination thereof. In some embodiments, the oil used is a siliconeoil.

In some suitable polydimethylsiloxane oils, all X1 groups are groupsthat are not hydrophilic. In some suitable polydimethylsiloxane oils,all X1 groups are alkyl groups. In some suitable polydimethylsiloxaneoils, all X1 groups are methyl. In some embodiments, every silicone oilis a polydimethylsiloxane oil in which all X1 groups are methyl. In somesuitable polydimethylsiloxanes, at least one unit has an X1 group thatis not methyl; if more than one non-methyl X1 unit is present, thenon-methyl X1 units may be the same as each other, or two or moredifferent non-methyl X1 units may be present. Polydimethylsiloxane oilsmay be end-capped with any of a wide variety of chemical groups,including, for example, hydrogen, methyl, other alkyl, or anycombination thereof. Also contemplated are cyclic polydimethylsiloxaneoils. Mixtures of suitable oils are also suitable.

In certain aspects, the aqueous-in-oil-in-aqueous double emulsioncomposition described herein is formulated as a sprayable formulation.In some embodiments, the formulation is diluted with a solvent. Incertain embodiments, the solvent comprises water. In certainembodiments, the solvent comprises sodium caseinate (NaCSn), lactose, ora combination thereof. In certain aspects, a method for co-injecting theaqueous-in-oil emulsion with water is applicable, wherein the ratio ofemulsion to water is from 1:1 to 1:100.

In another aspect, a method for preparing an aqueous-in-oil-in-aqueousdouble emulsion composition is provided. The method comprises (a)preparing an aqueous-in-oil emulsion composition using an aqueous phase,an oil phase, a lipophilic emulsifier, and an oil soluble thickener; (b)combining an active ingredient into the aqueous-in-oil emulsioncomposition; and (c) dispersing the aqueous-in-oil emulsion compositioninto a second aqueous phase. The previously described embodiments of theaqueous-in-oil-in-aqueous double emulsion composition are applicable tothe method for preparing an aqueous-in-oil-in-aqueous double emulsioncomposition described herein.

In various embodiments, the method further comprises addition of ahydrophilic emulsifier to the second aqueous phase. In some embodiments,the method further comprises addition of a surfactant to the secondaqueous phase.

In one aspect, a method of treating plants or plant parts is provided.The method of treating plants or plant parts comprises the step ofcontacting the plant or plant parts with an aqueous-in-oil-in-aqueousdouble emulsion as described herein. The previously describedembodiments of the aqueous-in-oil-in-aqueous double emulsion compositionand of the method for preparing an aqueous-in-oil-in-aqueous doubleemulsion composition are applicable to the method of treating plants orplant parts described herein. In another aspect, provided is a method ofinhibiting an ethylene response in plants or plant parts, comprisingapplying to the plants or plant parts an effective amount of the doubleemulsion composition disclosed herein or the diluted formulation fromsuch double emulsion composition.

In another embodiment, other agrochemical active ingredients can beadded to the water diluted water-in-oil emulsion of the presentinvention. Examples of agrochemical active ingredients suitable for usewithin the diluted water-in-oil emulsion include, those disclosed inU.S. Pat. No. 8,946,122, the content of which is incorporated byreference in its entirety.

Among embodiments in which plants are treated using methods involving acomposition of the present invention, the plants that are treated may beany plants that produce a useful product. Among embodiments in whichplant parts are treated using methods involving a composition of thepresent invention, the plant parts that are treated may be any part ofthe plant that produces a useful product. In some embodiments, usefulplant parts are treated with a method involving use of a composition ofthe present invention.

As used herein, to “treat” a plant or plant part means to bring theplant or plant part into contact with a material.

In embodiments of the present invention in which a plant or plant partis treated, a composition of the present invention is used in a way thatbrings cyclopropene into contact with the plant or plant part. In someembodiments, the method involves using a composition of the presentinvention in a way that releases cyclopropene from the cyclopropenemolecular encapsulating agent complex under conditions in which thecyclopropene then comes into contact with the plant or plant part.

For example, an embodiment of the composition of the present inventionmay be used in a process that brings cyclopropene into contact withplants or plant parts. Such contact may be performed in any of a widevariety of ways. For example, a embodiment of the composition of thepresent invention is placed in a closed space (such as, for example, atransportation trailer or a controlled-atmosphere room) along withplants or plant parts, and operations are performed on the compositionto promote the release of cyclopropene from the composition into theatmosphere of the closed space. Operations that promote the release ofcyclopropene from the composition include, for example, introducing gasbubbles into the composition.

For another example, an embodiment of the composition of the presentinvention may be placed in a closed space along with plants or plantparts, operations may be performed on the composition to promote therelease of cyclopropene from the composition into the atmosphere of theclosed space. Operations that promote the release of cyclopropene fromthe composition include, for example, contacting the composition of thepresent invention with water or with a high-humidity atmosphere.

In some embodiments, the practice of the present invention involvesbringing the cyclopropene molecular encapsulating agent complex intocontact with the plant or plant part. While the present invention is notlimited to any particular theory or mechanism, it is contemplated that,in embodiments in which a cyclopropene molecular encapsulating agentcomplex is brought into contact with a plant or plant part, some or allof the cyclopropene subsequently departs from the molecularencapsulating agent and, possibly after a diffusion process, comes intodirect contact with the plant or plant part.

For example, an embodiment of the composition of the present inventionmay be brought into contact with plants or plant parts directly. Someexamples of methods of such contact are, for example, spraying, foaming,fogging, pouring, brushing, dipping, similar methods, and combinationsthereof. In some embodiments, spraying or dipping or both is used. Insome embodiments, spraying is used. Such contact may be performedindoors or outdoors. In some of such embodiments, contact is performedon all or part of a plant while it is growing in a field (i.e., outdoorapplications). It is contemplated that the compositions provided can bemixed with water in a spray tank for indoor and/or outdoor (open field)applications.

Normally, a specific part of the plant forms the useful product. Aplurality of useful plant parts, after removal from a plurality ofplants, is known as a “crop.” Some types of plants have a single type ofuseful plant part, while other types of plants have plural types ofuseful plant parts.

Among the plants and plant parts that are suitable for use in thepresent invention, are, for example, plants (and parts thereof) withplant parts that are edible, plants (and parts thereof) with plant partsthat are non-edible but useful for some other purpose, and combinationsthereof. Also contemplated as suitable plants (and parts thereof) arethose from which useful materials can be extracted; such usefulmaterials may be, for example, edible materials, raw materials formanufacturing, medicinally useful materials, and materials useful forother purposes.

Further contemplated as suitable plants (and parts thereof) are thosethat yield plant parts that are useful for their beauty and/orornamental properties. Such ornamental plant parts include, for example,flowers and other ornamental plant parts such as, for example,ornamental leaves. Some of such plants produce useful bulbs. In someembodiments, an entire ornamental plant is considered to be the usefulplant part.

Plants that produce all types of edible plant parts are contemplated assuitable for use in the present invention. Also suitable are all typesof edible plant parts.

Many of the plants (and parts thereof) that are suitable for use in thepractice of the present invention can be usefully divided intocategories or groups. One useful method for defining such groups is the“Definition and Classification of Commodities,” published on or beforeMar. 23, 2006, by the Food and Agriculture Organization (“FAO”) of theUnited Nations as a “Draft.” In the practice of some embodiments of thepresent invention, it is contemplated to treat plants that produce oneor more crops that fall within any of the crop groups defined by theFAO. In some embodiments, it is contemplated to treat one or more cropsthat fall within one or more of those groups.

In a further aspect, provided is an aqueous-in-oil emulsion composition.The composition comprises:

(a) 20-80% by weight of an aqueous phase containing salt (APCS). TheAPCS comprises of water (10-50%), salt (10-60%), and a cyclodextrincomplex (5-20%). The complex is made up of cyclodextrin and a watersensitive agrochemically active ingredient (e.g., 1-MCP). The complexcan be made up of cyclodextrin and a water sensitive pharmaceuticallyactive ingredient or cyclodextrin and a water sensitive food activeingredient;(b) 20-80% by weight of an oil phase comprising an oil medium;(c) 0.05-20.0% by weight of a lipophilic emulsifier; and(d) 0-5% by weight of an oil soluble thickener.

The previously described embodiments of the aqueous-in-oil-in-aqueousdouble emulsion composition are applicable to the aqueous-in-oilemulsion composition described herein.

In another further aspect, provided is a secondaqueous-in-oil-in-aqueous double emulsion composition. The compositioncomprises:

(a) 5-20% by weight of an active ingredient;(b) 10-80% by weight of a first aqueous phase comprising at least onenon-deliquescent salt, wherein the ratio of dry weight of the salt toweight of the first aqueous phase is at least 0.2;(e) 10-80% by weight of an oil phase comprising an oil medium;(f) 0.05-20% by weight of a lipophilic emulsifier or hydrophobicemulsifier;(g) 0-5% by weight of an oil soluble thickener or a hydrophilicemulsifier; and(h) a second aqueous phase;wherein the by weight % does not consider the second aqueous phase.

The previously described embodiments of the firstaqueous-in-oil-in-aqueous double emulsion composition are applicable tosecond aqueous-in-oil-in-aqueous double emulsion described herein.

Those skilled in the art would understand certain variations can existbased on the disclosure provided. Thus, the following examples are givenfor the purpose of illustrating the invention and shall not be construedas being a limitation on the scope of the invention or claims.

EXAMPLES

Determining the 1-MCP concentration in a formulation: Approximately 120milligrams of formulation is accurately weighed into a 120 mL serumbottle using a disposable pipette. 3 mL of Milli Q water is added add tothe bottle. The bottle is capped with a crimp cap or Mininert valve.Using a gas tight syringe 0.25 mL of pure cis-2-butene is added to the0.25 mL to the bottle containing the sample. The bottle is placed on amulti-purpose rotator and the contents shaken for 30 minutes. A sampleof the headspace is analyzed by GC for 1-MCP concentration. This valueis then used to calculate the amount of 1-MCP in the originalformulation.

Determining the 1-MCP concentration in the headspace: Ten 100 mL Wheatonbrand serum bottles are filled with water and the volume measured. Theaverage volume of the ten bottles is 120 ml. 60 mL (which is 50% full)or 108 mL (which is 90% full) of the formulation is introduced into thebottle with the formulation being tested. A funnel is used to preventthe formulation from sticking to the neck of the bottle. The bottle issealed with a Mininert stopper that has a needle valve for sampling. Thebottle is placed on a multi-purpose rotator to agitate the throughoutthe experiment. A sample of the headspace is analyzed for 1-MCP usingisobutylene as an external standard.

Example 1

To prepare a stable W/O/W double emulsion, a stable water-in-oil (W/O)primary emulsion utilizing an effective hydrophobic (oil soluble)emulsifier is prepared first. Polyglycerol polyricinoleate (PGPR), afood grade additive, can be effective in emulsifying aqueous solutionscontaining salt, for example magnesium chloride (MgCl₂) solutions insoybean oil. These stable W/O emulsions can then be dispersed in water,using sodium caseinate as the hydrophilic emulsifier, to provide stableW/O/W double emulsions. Thus, using the W/O/W double emulsion approachit may be possible to make a stable W/O emulsion of HAIP in soybean oil(product concentrate) which could be further dispersed in water (W/O/W)to make a relatively stable double emulsion (low headspace for ˜3hours). Such double emulsion or formulation diluted with water can thenbe spray applied to fruit trees and other row crops.

The HAIP dispersion in water with magnesium sulfate (MgSO₄) is preparedand designated as the aqueous phase containing salt (APCS; for examplesee U.S. Pat. No. 8,691,728, the content of which is incorporated byreference). Exemplary preparations may contain 15-35% HAIP with 30-70%MgSO₄.7H₂O. W/O emulsions of APCS in soybean oil containing PGPR(Paalsgaard PGPR4125 as the hydrophobic emulsifier) is prepared anddesignated as the primary emulsion 1 (PE1). 8 g of PGPR is added to 92 gof soybean oil at 50° C. with stirring, and the PE1 solution is stirredfor 1 hour (BMS-7636). Next different amounts of APCS are added to thePE1 to prepare different samples. The samples are then homogenized for 2minutes.

TABLE 1 Water-in-oil emulsion with aqueous phase containing salt (APCS)Sample APCS BMS-7636 AI AI remaining ID (%) (%) (%) (7 days/54 C.)Comments BMS- 80 20 — — Very thick like cream 7637-80 cheese; Does notflow BMS- 70 30 0.74 73% Viscous 7637-70 BMS- 60 40 0.62 93% Viscous7637-60 BMS- 50 50 0.46 120%  Thick flowing liquid; 7637-50 No settlingBMS- 20 80 0.24 81% Free flowing liquid; 7637-20 Slight settling

Table 1 shows that emulsions of APCS in soybean oil can provide freeflowing liquids when the APCS content is ≤50% by weight. PGPR appears aneffective emulsifier in the oil. The emulsions are physically stable(very slight settling) and are chemically stable losing <20% AI whenstored at 54° C. for 1 week. This indicates that these formulations canbe stable for >12 months at ambient storage.

The amount of PGPR that would be needed to make stable emulsions is alsoinvestigated. 1, 4, and 8% PGPR in the soybean oil are tested with 20and 50% APCS in the emulsions, where the previous samples with 50% APCSare very thick and the previous samples with 20% APCS are much lessviscous. Although physically stable emulsions can be obtained with only1% PGPR, it seems that slightly higher loading (4%) of PGPR (WJZ6522-4and WJZ6525-4) provides better chemical stability.

TABLE 2 W/O emulsions with aqueous phase containing salt (APCS)containing different amounts of PGPR in the soybean oil 1-MCP (ppm) %1-MCP % PGPR in headspace 7 days at % AI Sample ID APCS:oil in oil (24h) Day 0 54° C. remaining WJZ6522-1 50:50 1 6721 0.60 0.43 71.1WJZ6522-4 4 5780 0.60 0.50 84.0 WJZ6522-8 8 5961 0.60 0.51 84.0WJZ6525-1 20:80 1 2889 0.21 0.17 73.9 WJZ6525-4 4 2905 0.22 0.18 78.3WJZ6525-8 8 3526 0.22 0.18 78.3

A modified aqueous phase containing salt (MAPCS) is also prepared byusing low amounts of polyvinyl alcohol (PVOH). One useful example of theMAPCS has 24% HAIP, 16.1% MgSO₄, and 1% PVOH (all by weight). W/Oemulsions are prepared using this MAPCS (Lot #BMS7643) as shown in Table3.

TABLE 3 W/O emulsions with modified aqueous phase containing salt(MAPCS) in soybean oil 1-MCP (ppm) % 1-MCP % PGPR in headspace 7 day at% AI Sample ID MAPCS:oil in oil (24 h) Day 0 54° C. remaining BMS7643-120:80 8 4585 0.17 0.02 11.8 BMS7643-2 50:50 8 6180 0.37 0.13 35.1

The extensive degradation of 1-MCP upon high temperature storageindicates that the droplets of MAPCS in the soybean oil are porous and1-MCP escapes into the oil phase where it degrades. This may be due tothe presence of the PVOH, which can behave as a hydrophilic surfactantand destabilize the water-oil interface. Since this process willaccelerate at higher temperatures, the storage stability tests arerepeated at a more conventional temperature of 40° C. with lower amountsof PGPR.

Although there is more AI retention at 40° C. compared to 54° C., therewill likely be still significant loss for these formulations to becommercially viable.

TABLE 4 W/O emulsions with modified aqueous phase containing salt(MAPCS) in soybean oil with lower amounts of PGPR % 1-MCP % PGPR 7 daysat 4 weeks at % AI Sample ID MAPCS:oil in oil Day 0 40° C. 40° C.remaining BMS7650-4 20:80 4 0.16 0.10 0.07 43.8 BMS7650-2 2 0.16 0.100.06 37.8 BMS7650-1 1 0.16 0.10 0.06 37.8 BMS7651-4 50:50 4 0.40 0.270.22 55.0 BMS7651-2 2 0.38 0.25 0.21 55.3 BMS7651-1 1 0.34 0.24 0.2058.8

W/O/W double emulsions for spraying can be prepared as follows. Forapplying a formulation, on row crops using commercial sprayers, the AIconcentration in the spray tank needs to be ≤1 g AI/L, or 0.1%. Theselow AI concentrations can be obtained by further dilutions of the W/Oemulsion. Sodium caseinate (NaCSn) and lactose can be added during W/O/Wdouble emulsion preparation to provide the minimum mixing between theinternal and external aqueous phases. Dilutions are made by adding theemulsion concentrates to water (containing different additives) withstirring, and results are shown in Table 5.

TABLE 5 Dilution of W/O emulsions containing HAIP Composition Ratio ofof aqueous Emulsion emulsion AI 1-MCP in headspace (ppm) Sample ID phaseconcentrate to water (%) 1 hour 3 hours WJZ6527B 12% NaCSn + WJZ6527SM1:4 0.11 9460 12,259 1% lactose WJZ6527D 12% NaCSn + WJZ6527SM 1:7 0.065073 7722 1% lactose WJZ6534A 12% NaCSn + WJZ6534SM 1:3 0.05 7,194 8,3441% lactose WJZ6534B 12% NaCSn + WJZ6534SM 1:1 0.07 4,944 5,833 1%lactose

The W/O emulsions used for the dilution experiments are:

WJZ6527SM=50:50 APCS/soybean oil containing 4% PGPR (0.60% AI)WJZ6534SM=20:80 APCS/soybean oil containing 4% PGPR (0.21% AI).

Table 5 shows that the 1:7 dilution of the 50:50 W/O emulsion(WJZ6527SM) provides a sprayable solution with 0.06% AI and lowconcentrations of 1-MCP in the headspace. The 20:80 W/O emulsion(WJZ6534SM) when added to water (containing 12% NaCSn and 1% lactose)provides very viscous materials (WJZ 6534A and WJZ 6534B).

By using a water-in-oil emulsion approach, it is possible to formulatestable dispersions of HAIP in oil that are chemically and physicallystable and have low AI content (0.2%). These emulsions can be sprayeddirectly or further diluted in water to create formulations that havevery low AI (0.05%) and low headspace concentration of 1-MCP.

Example 2

Additional water-in-oil (W/O) emulsions are prepared where the aqueousphase is APCS and the oil phase comprises a vegetable oil (for examplesoybean oil) or paraffin oils (for example Conosol 260 and/or Isopar V).Polyglycerol polyricinoleate (PGPR) is used as the hydrophobicemulsifier. The W/O emulsions can be diluted in water to provideformulations containing low (for example <0.1%) active ingredient (AI).These formulations can then be sprayed using standard sprayers typicallyused in farms and orchards.

4 g of PGPR is added to 96 g of oil (heated to 50° C. for soybean oil)with stirring (the primary emulsion 2 (PE2)), and the PE2 solution isstirred for 1 hour. The primary emulsion 3 (PE3) is prepared similarlyusing Conosol 260, and the primary emulsion 4 (PE4) is preparedsimilarly using Isopar V. An equal weight of the APCS is slowly added tothe PE2, PE3, and PE4, respectively. After all the APCS is added thedispersion is homogenized with an IKA (set at #2.5) for 3 minutes. TheAI concentration in these emulsions is −0.6% by weight. The headspaceconcentration is determined for all the three formulations.

A combination of whey protein isolate (WPI) and hydroxyethyl cellulose(HEC, Cellosize QP 100MH) as polysaccharides is used as the hydrophilicemulsifier in the water to generate stable W/O/W emulsions. A series of1:32 dilutions is prepared for different primary emulsions. The WPI andHEC are first combined with the water and then the primary emulsion isadded with mechanical stirring. The AI concentration in these dilutionsis ˜0.02% by weight.

An additional W/O/W double emulsion is prepared by adding 250 g of APCSto 250 g of Isopar V containing 4% PGPR. This mixture is thenhomogenized using an IKA (set at #2.5-3) for 20 minutes. The solvent(aqueous phase) used for dilution is prepared by adding CellosizeQP100MH (HEC) to well stirred Milli q water at 40° C. Stirring iscontinued for 40 minutes to dissolve the HEC. The stabilities of variousdilution preparations are recorded. If formation of two layers isobserved, the dilution is recorded as an unstable dispersion. Thesamples are then analyzed for AI content in triplicate. For headspacemeasurement, a 60 g aliquot is weighed in a 122 mL bottle. A headspacesample is taken after 1 hour, 3 hours and 5 hours, and analyzed for1-MCP.

TABLE 6 Aqueous phase containing salt (APCS) emulsified in differentoils with PGPR Viscosity 1-MPC in AI retention Sample ID Oil (mPa · s)headspace (10 days/54° C.) Physical stability BMS7666-B Soybean 39 7268ppm 85% Slight settling, (5h) easily dispersed BMS7663-4 Conosol 518,088 ppm   <1% Hard pack within 260 (3h) a few days BMS7667-2 Isopar13 2905 ppm 87% No settling V (5h)

Table 6 shows that using Isopar V as the oil phase (BMS7667-2) providesa stable emulsion with the lowest concentration of 1-MCP in theheadspace. On the other hand using Conosol 260 as the oil phase(BMS7663-4) provides an unstable emulsion which formed a hard pack aftera few days. In addition the concentration of 1-MCP in the headspaceis >18,000 ppm, which is not acceptable. The formulation using soybeanoil (BMS7666-B) gives a relatively stable emulsion (some settling onstorage) and low headspace concentration of 1-MCP. Since the soybean oilis viscous, the formulation is thick. The emulsions with soybean oil andIsopar V demonstrated high chemical stability with >85% AI remainingafter storage at 54° C. for 10 days. The emulsion made with Conosol 260loses all of the AI under the same conditions.

Table 7 shows that chemically and physically stable dilutions can begenerated using water containing a mixture of the hydrophilic surfactantWPI and HEC. Dilutions of the emulsion containing Conosol 260 generateformulations (BMS-7665-1, BMS-7665-2, and BMS-7665-3) having very high(>7000 ppm in 3 hours) 1-MCP concentrations in the headspace. Dilutingthe emulsion made with Isopar V (BMS-7667-2) with water, containing 2%WPI and 0.5% HEC, can generate a formulation which is physically stableand has low concentration of 1-MCP in the headspace (2870 ppm after 3hours).

TABLE 7 Aqueous phase containing salt (APCS) emulsions diluted in waterHeadspace 1-MCP W/O Additives concentration (ppm) Sample ID compositionDilution in water 1 hour 2 hour 5 hour Comments BMS-7665-1 APCS (50%)/1:32 0.5% 4983 7134 7430 No settling or Conosol 260 HEC + separation(50%) 2% WPI BMS-7665-2 APCS (50%)/ 1:32 0.5% 4270 — 13,359 No settlingor Conosol 260 HEC separation (50%) BMS-7665-3 APCS (50%)/ 1:32 2% WPI9085 8868 12,084 Phase Conosol 260 separation in (50%) 30 min BMS-7666-AAPCS (50%)/ 1:32 None 7060 9599 12,453 No Conosol 260 emulsification.(50%) Two phases BMS-7666-B APCS (50%)/ 1:32 0.5% 3384 5135 8824 Smalldroplets Soybean oil HEC + (50%) 2% WPI BMS-7667-1 APCS (50%)/ 1:32 None3519 3442 4499 No Soybean oil emulsification. (50%) Two phasesBMS-7667-2 APCS (50%)/ 1:32 0.5% 1174 2870 8253 No settling or Isopar VHEC + separation (50%) 2% WPI

To determine the optimum concentrations of WPI and HEC, a three-factortest is performed (dilution, WPI and HEC concentration being the threevariables) and the results are shown in Table 8, where responsesmeasured include 1-MCP concentration in the headspace, viscosity and thestability of the dispersion. A stable dispersion is recorded if no phaseseparation is observed after 3 hours.

Both the responses of 1-MCP concentration in the headspace and viscosityprovide statistically significant models with high R² values (>0.05). Nolack of fit is detected in these models. Only 4 out of the 15formulations are not stable and they are all from the experiments withthe HEC concentration equal to 0.05%.

TABLE 8 Diluting a APCS/Isopar V emulsion with water* 1-MCP in Dilutionheadspace Viscosity Exp # factor WPI (%) HEC (%) (ppm) (CPs) Stability 10.0313 4 0.05 3438 4 N 2 0.0313 2.5 0.3 2559 71 Y 3 0.0156 1 0.3 1190 55Y 4 0.0313 4 0.55 1517 557 Y 5 0.0313 1 0.05 2673 4 N 6 0.0625 4 0.33422 73 Y 7 0.0313 2.5 0.3 2334 58 Y 8 0.0156 4 0.3 1909 55 Y 9 0.06252.5 0.05 3088 5 N 10 0.0156 2.5 0.55 578 455 Y 11 0.0313 1 0.55 865 429Y 12 0.0625 2.5 0.55 1512 599 Y 13 0.0313 2.5 0.3 2361 43 Y 14 0.0625 10.3 3007 57 Y 15 0.0156 2.5 0.05 2496 5 N * 1/64 = 0.0156 (AI, 0.01%),1/32 = 0.0313 (AI, 0.02%), 1/16 = 0.062 (AI, 0.04%).

This response is not modeled because HPC concentration perfectlycorrelated with the stability result. The two models, generated from thedata, provide the following patterns: (a) higher dilution coupled with aHEC concentration of >0.33% can provide a formulation with lowheadspace; (b) a WPI concentration of ≥1% is required; and (c) if aheadspace concentration of 1500 ppm and a viscosity of 400 CPs aredesired, the model can predict many different combinations of dilutionsand WPI to achieve that. A laboratory spray experiment has shown thatthe sample from Experiment #10 (Table 8), which has a viscosity of 455,can be sprayed readily.

Example 3

An aqueous phase containing salt (APCS) is used as the water phase andIsopar V as the oil phase. 300 g of APCS is added to a beaker. 300 g ofIsopar V (Exxon Mobil, lot #67369), containing 4% (by weight) PGPR, isadded. This mixture is then homogenized at room temperature using an IKAUltra Turrax (set at #2.5) for 5 minutes. A flowable mixture is formedimmediately upon blending of the sample. 0.63% 1-MCP is detected in theW/O emulsion.

2.5% WPI in the water together with 0.55% of the thickener (CellosizeQP100MH (HEC)) can provide low headspace concentrations. Since thelowest level of WPI in the DOE is 1%, lower levels of WPI are chosen forevaluation.

The data in Table 9 suggest that lower levels of WPI provide lowerrelease of 1-MCP in the headspace. Using 0.5% WPI (Expt. #2) results ina slight increase in the release of 1-MCP.

TABLE 9 Effect of WPI concentration on the headspace concentration of1-MCP Dilution HEC in WPI in AI 1-MCP in headspace (ppm) Exp # Ratiowater (%) water (%) (%) 1 hour 3 hours 5 hours 1 1:59 0.55 2.5 — 13,67014,131 14,653 2 1:59 0.55 0.5 0.017 6,509 10,316 11,711 3 1:59 0.55 1.00.019 3,341 8,876 10,985

To gently stirred tap water is first added the surfactant followed bythe thickener. The thickener is added slowly, and stirring is continuedfor ˜20 minutes for complete dissolution. The W/O emulsion from above isthen added. A stable dispersion is obtained. Since the highestconcentration of 1-MCP is when the container is full (i e minimum airvolume) all the headspace data reported are measured with the container90% full and with constant agitation.

To investigate if WPI can be replaced, four different surfactants withdifferent HLB values are evaluated. The results from the evaluations areshown in Table 10.

Pluronic L-35 (a PEG-PPG-PEG tri-block polymer from BASF) is thesurfactant which provides the least amount of 1-MCP release (i.e. thelowest headspace concentration of 1-MCP) when used at 0.5% (Expt#WJZ6620B). After >3 h of agitation, the headspace concentrationincreases to 13,000 ppm. This study indicates that WPI can be replacedwith other widely used surfactants to provide stable dispersions of APCSwith low headspace concentrations of 1-MCP. The use of WPI does provideless 1-MCP in the headspace compared to the other surfactants tested.

TABLE 10 Release of 1-MCP in the presence of different surfactants HECHLB 1-MCP in headspace (ppm) 90% full Exp # (%) Surfactant (%) value 1hour 3 hours 5 hours WJZ6618B 0.55 Tween 80 (1.0%) 15 10,651 12,88314,484 WJZ6618B 0.55 Tween 80 (0.5%) 15 8,943 12,198 13,945 WJZ6619A0.55 SLS (1.0%) 40 10,305 10,141 11,313 WJZ6619B 0.55 SLS (0.5%) 4013,115 13,393 13,971 WJZ6620A 0.55 Pluronic L-35 (1.0%) 18-23 10,69614,561 17,388 (PEG-PPG-PEG) WJZ6620B 0.55 Pluronic L-35 (0.5%) 18-235,573 12,992 13,815 WJZ6621A 0.55 Pluronic 10R5 (1.0%) 12-18 9,89613,651 15,614 (PPG-PEG-PPG) WJZ6621B 0.55 Pluronic 10R5 (0.5%) 12-188,091 11,445 13,024

Example 4

Further investigations were performed regarding dispersion ofaqueous-in-oil emulsions containing HAIP. To this end, varioushydrophilic emulsifiers and polymeric surfactants were evaluated fortheir effects on dispersion of the emulsion and their effects on theconcentration of 1-MCP in the headspace of a container.

In the instant example, AF10064K (a water-in-oil emulsion) was dilutedwith water (1:59; 0.01% 1-MCP), optionally containing hydroxyethylcellulose (HEC) at varying concentrations. Headspace was measured asdescribed previously. The results from the evaluations are shown inTable 11.

The headspace values for 1-MCP in the evaluated dispersions wereadvantageously low. Inclusion of HEC in the composition was beneficialfor dispersing AF10064K. However, the dispersion phase separatedimmediately upon standing, and droplets stuck to the wall of thecontainer.

TABLE 11 Release of 1-MCP and dispersion characteristics with HEC addedto dilution Dilution 1-MCP in headspace (ppm) 90% full Exp # ratio AI(%) HEC (%) 1 hour 3 hours 5 hours Comments BMS-7734-A 1:59 0.01 — 4,0214,585 5,282 No dispersion BMS-7730-A 1:59 0.01 0.55 2,406 5,619 6,651Small droplets. No phase stability BMS-7735-A 1:59 0.01 0.28 2,518 4,2944,427 Small droplets. No phase stability

Example 5

To improve dispersibility, a nonionic surfactant was also added to thedispersion. In the instant example, various surfactants with differentdegrees of hydrophilic/lipophilic balance (HLB). In the instant example,HEC was added at 0.3%, and one of the following surfactants were added:i) Pluronic L-35 (0.1%), with an HLB value between 18-23; ii) Tween 80(0.1%), with an HLB value of 15; or iii) Tween 85 (0.1%), with an HLBvalue of 11. Headspace was measured as described previously. The resultsfrom the evaluations are shown in Table 12.

The addition of a surfactant to the dispersion provided an improvedeffect on the double emulsions. As shown in Table 12, addition of Tween85 to the dispersion provided a desirably low headspace value for 1-MCPand a fair dispersion of the resultant composition.

TABLE Release of 1-MCP and dispersion characteristics with surfactants(HLB 18-23) added to dilution HEC 1-MCP in headspace (ppm) 90% fullDispersion Exp # (%) Surfactant HLB 1 hour 3 hours 5 hours CommentsBMS7749-C 0.3 Pluronic 18-23 11,002 16,360 17,773 Fair L-35 (0.1%)BMS7749-G 0.3 Tween 80 15 19,592 26,566 25,203 Good (0.1%) BMS7749-L 0.3Tween 85 11 2153 4804 6681 Fair (0.1%)

Example 6

Further nonionic surfactants were subsequently tested. To furtherdecrease the headspace concentration, a surfactant would be requiredthat would be able to provide more steric stabilization in addition toelectronic stabilization. Tween 85 is a small molecule (MW=428) andhence its ability to stabilize a surface via steric interactions issomewhat limited.

In the instant example, various polymeric surfactants with an HLB valuebetween 11-15 were tested from the styrene-maleic anhydride copolymerssold by Cray Valley (a subsidiary of Total). For the instant example,polymeric surfactants of the following formula were tested:

In the instant example, HEC was added at 0.3%, and one of the followingsurfactants were added: i) SMA 2625H (0.08% of solids), with an HLBvalue of 13.8; ii) SMA 3000H (0.04% of solids), with an HLB value of12.3; or iii) SMA 1440H (0.1% of solids), with an HLB value of 14.4.Headspace was measured as described previously. The results from theevaluations are shown in Table 13.

The addition of polymeric surfactants with an HLB value of 11-15 to thedispersion unexpectedly provided a synergistic effect between thehydrophilic emulsifier and the surfactant. As shown in Table 13,polymeric surfactants with an HLB value between 11-15 to the dispersionprovided a desirably low headspace value for 1-MCP and a good dispersionof the resultant composition. Addition of the surfactant SMA 3000H(HLB=12.3) resulted in a desirably low 1-MCP in the headspace and provedto be the most effective dispersant.

TABLE 13 Release of 1-MCP and dispersion characteristics with polymericsurfactants added to dilution Polymer 1-MCP in headspace (ppm) 90% fullDispersion Exp # (% solids) R HLB 1 hour 3 hours 5 hours Comments WJZ6663 SMA Butyl 13.8 567 1,089 1,465 Good 2625H (0.08%) WJZ 6668 SMA H12.3 476 878 1,253 Good 3000H (0.04%) WJZ 6670 SMA Butyl 14.4 810 1,2521,494 Good 1440H (0.1%)

Subsequently, SMA® 2625H (HLB value=13.8) and SMA® 3000H (HLBvalue=12.3) were further tested. AF10064K (water-in-oil emulsion) wasdiluted with water (1:59, 0.01% 1-MCP) containing HEC and either SMA®2625H or SMA® 3000H. Headspace was measured as described previously. Theresults from the evaluations are shown in Table 14.

As shown in Table 14, polymeric surfactants are very efficient indispersing AF10064K in water with low 1-MCP concentration in theheadspace. Since SMA® 2625H has 25% solids and SMA® 3000H has only 15%solids, the amount of polymer required is <0.1%. The SMA® 3000H, withthe lowest HLB, is more efficient providing stable dispersions ofAF10064K with <3000 ppm of 1-MCP in the headspace, even after 5 hours.

TABLE 14 Release of 1-MCP and dispersion characteristics with SMA ®2625H and SMA ® 3000H surfactants added to dilution HEC Surfactant 1-MCPin headspace (ppm) 90% full Dispersion Exp # (%) HLB 1 hour 3 hours 5hours Comments BMS7752-2 0.3 SMA ® 2625H (0.3) 2,571 3,300 4,900 Largedroplets. Phase separation over time. BMS7757-2 0.3 SMA ® 3000H (0.3)2787 2884 2448 Small droplets. Some phase separation BMS7757-3 0.3 SMA ®3000H (0.5) 962 1131 1227 Small droplets. Stable dispersion BMS7757-40.3 SMA ® 3000H (0.8) 1075 1371 1531 Small droplets. Stable dispersion

1.-20. (canceled)
 21. An aqueous-in-oil emulsion composition comprisingan aqueous phase containing salt (APCS).
 22. The aqueous-in-oil emulsioncomposition of claim 21, wherein the APCS comprises water.
 23. Theaqueous-in-oil emulsion composition of claim 21, wherein the APCScomprises water at an amount selected from the group consisting of morethan 20% water by weight, more than 30% water by weight, more than 50%water by weight, and more than 60% water by weight (based on the weightof the composition).
 24. The aqueous-in-oil emulsion composition ofclaim 21, wherein the APCS comprises one or more salts.
 25. Theaqueous-in-oil emulsion composition of claim 24, wherein no chloridesalt is used.
 26. The aqueous-in-oil emulsion composition of claim 24,wherein the salt is a non-deliquescent salt.
 27. The aqueous-in-oilemulsion composition of claim 24, wherein the salt comprises magnesiumsulfate or ammonium sulfate.
 28. The aqueous-in-oil emulsion compositionof claim 27, wherein the ratio of dry weight of the salt to weight ofthe aqueous phase of the aqueous-in-oil emulsion composition is at least0.25.
 29. The aqueous-in-oil emulsion composition of claim 27, whereinthe ratio of the dry weight of salt to the weight of water is selectedfrom the group consisting of 0.05 or higher; or 0.1 or higher; or 0.2 orhigher; or 0.3 or higher; or 0.35 or higher.
 30. The aqueous-in-oilemulsion composition of claim 21, wherein the molecular complex of anencapsulated volatile compound comprises a cyclopropene molecularencapsulating agent complex.
 31. The aqueous-in-oil emulsion compositionof claim 21, wherein the APCS comprises 1-methylcyclopropene (1-MCP).32. The aqueous-in-oil emulsion composition of claim 31, wherein the1-MCP is present in a molecular complex distributed throughout theaqueous-in-oil emulsion composition.
 33. The aqueous-in-oil emulsioncomposition of claim 32, wherein the molecular complex comprisesalpha-cyclodextrin.
 34. The aqueous-in-oil emulsion composition of claim21, wherein the aqueous-in-oil emulsion composition comprises at least5%, at least 10%, at least 20%, at least 30%, at least 40%, at least50%, or at least 60% by weight of a complex of 1-methylcyclopropene(1-MCP) and alpha-cyclodextrin.
 35. The aqueous-in-oil emulsioncomposition of claim 21, wherein the aqueous-in-oil emulsion compositioncomprises an oil phase comprising an oil medium.
 36. The aqueous-in-oilemulsion composition of claim 35, wherein the oil medium is selectedfrom the group consisting of soybean oil, hydrogenated soybean oil,cotton seed oil, hydrogenated cotton seed oil, white mineral oil,hydrotreated middle petroleum distillate, hydrotreated light petroleumdistillate, and combinations thereof.
 37. The aqueous-in-oil emulsioncomposition of claim 35, wherein the aqueous-in-oil emulsion compositioncomprises 10-20%; 20-40%; 40-60%; 15-30%; or 30-55% by weight of the oilphase.
 38. The aqueous-in-oil emulsion composition of claim 31, whereinthe 1-MCP is present at a concentration of <4 g/L of the emulsioncomposition.
 39. The aqueous-in-oil emulsion composition of claim 21,wherein no appreciable amount of calcium chloride is present in theaqueous-in-oil emulsion composition.
 40. An aqueous-in-oil-in-aqueousdouble emulsion composition comprising i) an aqueous-in-oil emulsioncomposition comprising an aqueous phase containing salt (APCS) and ii) asecond aqueous phase.